Garnet materials for li secondary batteries and methods of making and using garnet materials

ABSTRACT

Set forth herein are garnet material compositions, e.g., lithium-stuffed garnets and lithium-stuffed garnets doped with alumina, which are suitable for use as electrolytes and catholytes in solid state battery applications. Also set forth herein are lithium-stuffed garnet thin films having fine grains therein. Disclosed herein are novel and inventive methods of making and using lithium-stuffed garnets as catholytes, electrolytes and/or anolytes for all solid state lithium rechargeable batteries. Also disclosed herein are novel electrochemical devices which incorporate these garnet catholytes, electrolytes and/or anolytes. Also set forth herein are methods for preparing novel structures, including dense thin (&lt;50 um) free standing membranes of an ionically conducting material for use as a catholyte, electrolyte, and, or, anolyte, in an electrochemical device, a battery component (positive or negative electrode materials), or a complete solid state electrochemical energy storage device. Also, the methods set forth herein disclose novel sintering techniques, e.g., for heating and/or field assisted (FAST) sintering, for solid state energy storage devices and the components thereof.

CROSS-REFERENCES TO RELATED

This application claims priority to U.S. Provisional Patent ApplicationNo. 61/887,451, filed Oct. 7, 2013, entitled METHOD AND SYSTEM FORFORMING GARNET MATERIALS WITH SINTERING PROCESS, and U.S. ProvisionalPatent Application No. 61/926,910, filed Jan. 13, 2014, entitled GARNETTHIN FILM ELECTROLYTE, and U.S. Provisional Patent Application No.62/007,417, filed Jun. 4, 2014, entitled METHODS AND SYSTEMS FOR FORMINGGARNET MATERIAL WITH REACTIVE SINTERING, and U.S. Provisional PatentApplication No. 62/026,271, filed Jul. 18, 2014, entitled FINE GRAINEDLITHIUM-ION CONDUCTING THIN FILM GARNET CERAMICS, and U.S. ProvisionalPatent Application No. 62/026,440, filed Jul. 18, 2014, entitled GARNETCATHOLYTE AND SINTERING OF SOLID STATE ELECTROCHEMICAL DEVICES ANDCOMPONENTS. Each of these provisional patent applications isincorporated by reference herein for all purposes in their entirety.

BACKGROUND OF THE INVENTION

Cleaner forms of storing energy are in great demand. Examples of cleanenergy storage include rechargeable lithium (Li) ion batteries (i.e.,Li-secondary batteries), in which Li⁺ ions moves from the negativeelectrode to the positive electrode during discharge. In numerousapplications (e.g., portable electronics and transportation), it isadvantageous to use a solid state Li ion battery which consists of allsolid state materials as opposed to one that includes liquid components,(e.g., flammable liquid electrolytes), due to safety as well as energydensity considerations. Solid state Li ion batteries which incorporate aLi-metal negative electrode advantageously also have significantly lowerelectrode volumes and correspondingly increased energy densities.

Critically important components of a solid state battery include theelectrolyte, which electrically isolates the positive and negativeelectrodes, and, often, also a catholyte, which is intimately mixed witha positive electrode active material to improve the ionic conductivitytherein. A third important component, in some Li ion batteries, is ananolyte which is laminated to, or in contact with, an anode material(i.e., negative electrode material; e.g., Li-metal). Currently availableelectrolyte, catholyte, and anolyte materials, however, are not stablewithin solid state battery operating voltage ranges or when in contactwith certain cathode or anode active materials (e.g., metal fluorides).

Garnet (e.g., Li-stuffed garnet) is a class of oxides that has thepotential to be suitable for use as a catholyte, electrolyte, and, or,anolyte in an all solid state battery. However, garnet materials haveyet to be prepared with the proper morphology (e.g., thin film ornanostructured powder) or with sufficient conductivity and, or, particleconnectivity to function sufficiently well. Certain garnet materials andprocessing techniques are known (e.g., U.S. Pat. Nos. 8,658,317,8,092,941, and 7,901,658; U.S. Patent Application Publication Nos.2013/0085055, 2011/0281175, 2014/0093785, and 2014/0170504; alsoBonderer, et al. “Free-Standing Ultrathin Ceramic Foils,” Journal of theAmerican Ceramic Society, 2010, 93(11):3624-3631; and Murugan, et al.,Angew Chem. Int. Ed. 2007, 46, 7778-7781) but these materials andtechniques suffer from a variety of deficiencies such as, but notlimited to, insufficient conductivity or processing conditions which areincompatible with certain solid state battery components.

Accordingly, there is a need for improved methods of making andprocessing garnet materials, particularly with regard to the integrationof garnet films and powders with cathode active material in all solidstate batteries. The following disclosure provides, in part, manysolutions to these as well as to other problems in the relevant field towhich the instant disclosure relates.

BRIEF SUMMARY OF THE INVENTION

Disclosed herein are novel and inventive methods of making and usingthin film and powder morphologies of lithium-stuffed garnets ascatholytes, electrolytes, and anolytes, for solid statelithium-secondary batteries. Also disclosed herein are novel garnetcatholytes, electrolytes, and anolytes as well as novel electrochemicaldevices which incorporate these materials. In contrast to known garnets,the methods and materials set forth herein are uniquely designed forelectrochemical devices (e.g., solid state batteries) and havemorphologies, conductivities, densities, porosities, and surfaceproperties (e.g., roughness, flatness, lack of surface cracks anddefects), and chemical, temperature and voltage stabilities suitable foruse in lithium batteries.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an illustration of liquid phase sintering according to theflux sintering methods set forth herein.

FIG. 2 shows a plot of partial oxygen pressure as a function ofcalcination temperature for preparing certain calcined oxides.

FIG. 3 shows a trilayer battery component wherein a metal layer (e.g.,metal powder or foil) is positioned between and in contact with twoelectrolyte (e.g., Li-stuffed garnet) layers.

FIG. 4 shows a method of calcining or sintering garnet particles, orgarnet-metal-garnet trilayers set forth herein, including applyingpressure to the layer(s) during the calcining or sintering step usingplates, which can be dye or setter plates.

FIG. 5 shows an example method of calcining or sintering a garnet layer(e.g., garnet bi-layer, tri-layer, garnet-active-material compositelayer), wherein the weight of the Dye (or setter) plates provides theonly external pressure applied to the calcining or sintering layer.

FIG. 6 shows scanning electron microscopy (SEM) and focused ion-beam(FIB) microscopy of thin film garnet films made by the reactivesintering methods set forth herein using applied pressure but withoutusing additional lithium source powders.

FIG. 7 shows an x-ray diffraction (XRD) pattern (Intensity on y-axis,2-theta on x-axis) for thin film garnet film made by reactive sinteringat about 1150° C. and without the use of additional lithium sourcepowder. Labeled peaks [(112), (312), (400), (204), (224)] correspond tocrystal phase for Li₇La₃Nb₂O₁₃.

FIG. 8 shows a dense garnet thin film prepared by reactive sinteringwith applied pressure. Scale bar for left image is 10 μm. Scale bar forright image is 100 μm.

FIG. 9 shows a conductivity phase space map ofLithium-Lanthanum-Zirconia-Alumina, prepared according to the methodsset forth herein, and showing the total conductivity (at 20° C.) forseveral different processing temperature/time combinations as a functionof Li and Al in Li_(x)La₃Zr₂O₁₂.yAl₂O₃, wherein x ranges from 5.5 to 9(plot x-axis is from 5.5 to 9.0); and y ranges from 0 to 1 (plot y-axisis from 0 to 2). Left image is for materials processed at 1075° C.;Middle image is for materials processed at 1150° C.; Right image is formaterials processed at 1200° C.

FIG. 10 shows grain sizes (top plots), density (middle plots), andconductivity (bottom plots) and as a function of Li content inLi_(x)La₃Zr₂O₁₂.yAl₂O₃, wherein x ranges from 5.5 to 9; and y rangesfrom 0 to 1, and processing temperature/time. Compositions marked A, B,C, and D were sintered at 1075° C. for 6 hours and possesses both smallgrain size and conductivity >10⁻⁴ S/cm. Composition A is characterizedby Li_(6.3)La₃Zr₂O₁₂.0.35Al₂O₃; Composition B is characterized byLi_(6.3)La₃Zr₂O₁₂.0.67Al₂O₃; Composition C is characterized byLi₇La₃Zr₂O₁₂.0.67Al₂O₃; Composition D is characterized byLi₇La₃Zr₂O₁₂.Al₂O₃. These composition subscripts and molar coefficientsdescribe the respective amount of raw materials used to prepare thesecompositions.

FIG. 11 shows Lithium-Lanthanum-Zirconia-Alumina comparative exampleswith comparison to the inventive compositions A, B, C, and D set forthherein. Composition A is characterized by Li_(6.3)La₃Zr₂O₁₂.0.35Al₂O₃;Composition B is characterized by Li_(6.3)La₃Zr₂O₁₂0.67Al₂O₃;Composition C is characterized by Li₇La₃Zr₂O₁₂.0.67Al₂O₃; Composition Dis characterized by Li₇La₃Zr₂O₁₂.Al₂O₃. These composition subscripts andmolar coefficients describe the respective amount of raw materials usedto prepare these compositions.

FIG. 12 shows scanning electron microscopy images of lithium stuffedgarnet films, Li_(x)La₃Zr₂O₁₂.yAl₂O₃, wherein x ranges from 5.5 to 9;and y ranges from 0 to 1, prepared by heat sintering at 1075° C. andhaving variable Li:Al amounts.

FIG. 13 shows conductivity plots as a function of Li:Al amounts in thelithium stuffed garnets films set forth herein, Li_(x)La₃Zr₂O₁₂.yAl₂O₃,wherein x ranges from 5.5 to 9; and y ranges from 0 to 1.

FIG. 14 shows density plots as a function of Li:Al amounts in thelithium stuffed garnets films set forth herein, Li_(x)La₃Zr₂O₁₂.yAl₂O₃,wherein x ranges from 5.5 to 9; and y ranges from 0 to 1, and whereinthe films are heat sintered at 1075° C., 6 hours, (left plot), 1150° C.,6 hours, (middle plot), or 1200° C., 15 minutes (right plot). (x-axisranges from 5.0 to 9.0; y-axis, in each plot, ranges from 0 to 2.0)

FIG. 15 shows an example of sintering a cylindrical form factormaterial.

FIG. 16 shows a film sintered by a sintering system wherein sinteringelectrodes electrically contacts the film at two positions on the filmsurface.

FIG. 17 shows a film sintered with setter plates that have individuallyaddressable electrical contact points.

FIG. 18 shows an example of sintering a film using calender rollers thatconduct an electrical current.

FIG. 19 shows an example of sintering a film using calender rollerswherein one roller has individually addressable electrical contactpoints and the other roller is a ground electrode.

FIG. 20 shows a film sintered with sintering plates wherein one or moremetal foils are inserted between the sintered film and the setterplates.

FIG. 21 shows a film sintered with sintering plates wherein one or moremetal powders are inserted between the sintered film and the setterplates.

FIG. 22 shows a film sintered with calender rollers wherein one rolleris a spiral design that is movable so that the points of contact betweenthe spiral roller and the thin film can controllably be moved during thesintering process.

FIG. 23 shows examples of films and rectangular form factors (e.g., thinfilms) that can be sintered according to the methods set forth herein.

FIG. 24 illustrates sintering wherein a current is conducted through asintering film.

FIG. 25 shows a method of making an embodiment of an invention disclosedherein.

FIG. 26 shows an example composite electrode, prepared according to themethods set forth herein, for a solid state battery composed of activeelectrode materials with interspersed electrolyte particles prior to anysintering treatment. The layer can also contain an electricallyconductive additive (e.g. carbon) (not shown).

FIG. 27 shows a schematic of an example fully sintered solid statecomposite electrode.

FIG. 28 shows an arrangement for FAST sintering of an electrolytemembrane for use in a Li-ion solid state battery.

FIG. 29 shows an arrangement for FAST sintering of anelectrolyte-cathode combination which would operate as a solid statebattery.

FIG. 30 shows a scanning electron microscopy (SEM) image of a freestanding film prepared according to a method described herein. Scale baris 100 μm. Arrows point to end edge boundaries. Film is imaged edge-on.

FIG. 31 shows a SEM image of a 40 micron thick free standing (i.e., nosubstrate) garnet membrane (left side) prepared by sintering theunsintered film between supporting setter plates also composed of garnetmaterial. FIG. 31 (right side) also shows a magnified portion of theimage on the left side.

FIG. 32 shows the particle size distribution of garnet precursor powdersbefore and after milling.

FIG. 33 shows the particle size distribution of Lithium Hydroxide andLanthanum Oxide powders before milling.

FIG. 34 shows the particle size distribution of Lithium Hydroxide andLanthanum Oxide after milling.

FIG. 35 shows cross sectional SEM of a garnet film bilayer formed bysintering garnet powder. The top layer is Ni (nickel) and the bottomlayer is a lithium stuffed garnet. Scale bar is 30 μm.

FIG. 36 shows conductivity plots for the bilayer of FIG. 35.

FIG. 37 show reaction sintered Li₇La₃Zr₂O₁₂ using 100% lithium stuffedgarnet precursors. Scale bar for top left image is 100 μm; Scale bar fortop right image is 10 μm; Scale bar for bottom image is 10 μm. Filmprepared by doctor-blading with 5 mil slot gap.

FIG. 38 shows reaction sintered Li₇La₃Zr₂O₁₂ using 75% w/w lithiumstuffed garnet precursors and 25% w/w lithium stuffed garnet powder.Scale bar for top left image is 100 μm; Scale bar for top right image is10 μm; Scale bar for bottom image is 5 μm. Film prepared bydoctor-blading with 5 mil slot gap.

FIG. 39 shows reaction sintered Li₇La₃Zr₂O₁₂ using 50% w/w lithiumstuffed garnet precursors and 50% w/w lithium stuffed garnet powder.Scale bar for top left image is 100 μm; Scale bar for top right image is10 μm; Scale bar for bottom image is 10 μm. Film prepared bydoctor-blading with 5 mil slot gap.

FIG. 40 shows reaction sintered Li₇La₃Zr₂O₁₂ using 25% w/w lithiumstuffed garnet precursors and 75% w/w lithium stuffed garnet powder.Scale bar for top left image is 100 μm; Scale bar for top right image is10 μm; Scale bar for bottom image is 5 μm. Film prepared bydoctor-blading with 5 mil slot gap.

FIG. 41 shows reaction sintered Li₇La₃Zr₂O₁₂ using 75% w/w lithiumstuffed garnet precursors and 25% w/w lithium stuffed garnet powder.Scale bar for top left image is 100 μm; Scale bar for top right image is10 μm; Scale bar for bottom image is 5 μm. Film prepared bydoctor-blading with 10 mil slot gap.

FIG. 42 shows reaction 10 mil sintered Li₇La₃Zr₂O₁₂ using 50% w/wlithium stuffed garnet precursors and 50% w/w lithium stuffed garnetpowder. Scale bar for top left image is 100 μm; Scale bar for top rightimage is 10 μm; Scale bar for bottom image is 5 μm. Film prepared bydoctor-blading with 10 mil slot gap.

FIG. 43 shows reaction sintered Li₇La₃Zr₂O₁₂ using 25% w/w lithiumstuffed garnet precursors and 75% w/w lithium stuffed garnet powder.Scale bar for top left image is 100 μm; Scale bar for top right image is10 μm; Scale bar for bottom image is 10 μm. Film prepared bydoctor-blading with 10 mil slot gap.

FIG. 44 diagrams various layer architectures that can be sinteredaccording to the sintering methods set forth herein: A) free-standinglithium stuffed garnet material; B) free-standing lithium stuffed garnetmaterial which optionally includes an active material, a binder, asolvent, and, or, carbon; C) a bilayer having one layer of a lithiumstuffed garnet and one layer of a metal powder, foil or sheet; D) abilayer having one layer of a lithium stuffed garnet material whichoptionally includes an active material, a binder, a solvent, and, or,carbon and one layer of a metal powder, foil, or sheet; E) a trilayerhaving two layers of a lithium stuffed garnet and one layer of a metalpowder, foil or sheet, between and in contact with the garnet layers;and F) a trilayer having two layers of a lithium stuffed garnet materialwherein each garnet layer optionally includes an active material, abinder, a solvent, and, or, carbon and one layer of a metal powder,foil, or sheet, between and in contact with the garnet layers.

FIG. 45 shows a sintering method wherein sintering electrodeselectrically contacting the film are deposited or sputtered at twopositions on the film surface to pass a current therebetween.

FIG. 46 shows an optical picture of a dense and freestanding garnet filmpellet and also a SEM image of the free standing film.

FIG. 47 shows the conductivity plot for the film in the SEM of FIG. 46having a Ni backing.

FIG. 48 shows plating/stripping at high current density for the film ofFIG. 46.

FIG. 49 shows and x-ray diffraction pattern (XRD) for composition C.

FIG. 50 shows an impedance spectrum for a pellet of composition Cmeasured at 30° C.

FIG. 51 shows a charge discharge curve for an electrochemical cellhaving a pellet of composition C as an electrolyte which was cycled at20 μA/cm².

FIG. 52 shows a plot of Density (g/cm) as a function of flux volumepercent for a 1:1 molar mixture of Li₂CO₃ and B₂O₃.

FIG. 53 shows an impedance spectrum for a lithium stuffed garnet bilayer(garnet-Ni).

FIG. 54 shows a low magnification SEM images of bilayers prepared undervarying partial pressure oxygen conditions (scale bar in each image is100 μm).

FIG. 55 shows a high magnification SEM images of garnet-nickel bilayersprepared under varying partial pressure oxygen conditions (scale bar ineach image is 20 μm).

FIG. 56 shows SEM images of garnet-nickel bilayers prepared undervarying partial pressure oxygen conditions (scale bar in each image intop and bottom row is 100 μm; scale bar in each image in middle row is20 μm).

FIG. 57 shows SEM images of FAST sintered lithium stuffed garnet powder.(Left Top and Bottom—800° C.; 3 Amps preparation) (Right Top andBottom—800° C.; 2 Amps preparation) (100 μm scale bars in Top left andTop Right) (10 μm scale bars in Bottom left and right)

FIG. 58 shows a SEM images of FAST sintered lithium stuffed garnetpowder. (Left Top and Bottom—800° C.; 2 Amps preparation) (Right Top andBottom—900° C.; 2 Amps preparation) (100 μm scale bars in Top left andTop Right) (10 μm scale bars in Bottom left and right)

FIG. 59 shows a half-cell experimental set-up with a garnet-Nickelbilayer electrolyte.

FIG. 60 shows a free standing lithium stuffed garnet film.

FIG. 61 shows a electrochemical impedance spectroscopy (EIS, y-axis isimaginary impedance in Ω, x-axis is real impedance in Ω) for lithiumstuffed garnet comparing Pt setter plates to ceramic setter plates and alower area specific resistance (ASR) for lithium stuffed garnet preparedby a sintering method using ceramic setter plates.

FIG. 62 shows impedance comparison for sintering pellets in Ar, inAr/H₂, or in Air.

FIG. 63 shows EIS, showing less than 10 Ωcm² for free standing film ofFIG. 46, wherein the film was cut to a 13 mm disc with 7 mm diameter Lideposited thereupon.

DETAILED DESCRIPTION OF THE INVENTION

The following description is presented to enable one of ordinary skillin the art to make and use the inventions set forth herein and toincorporate these inventions in the context of particular applications.Various modifications, as well as a variety of uses in differentapplications will be readily apparent to those skilled in the art, andthe general principles defined herein may be applied to a wide range ofembodiments. Thus, the present invention is not intended to be limitedto the embodiments presented, but is to be accorded the widest scopeconsistent with the principles and novel features disclosed herein.

The reader's attention is directed to all papers and documents which arefiled concurrently with this specification and which are open to publicinspection with this specification, and the contents of all such papersand documents are incorporated herein by reference. Unless expresslystated otherwise, each feature disclosed is one example only of ageneric series of equivalent or similar features.

Furthermore, any element in a claim that does not explicitly state“means for” performing a specified function, or “step for” performing aspecific function, is not to be interpreted as a “means” or “step”clause as specified in 35 U.S.C. Section 112, Paragraph 6. Inparticular, the use of “step of” or “act of” in the Claims herein is notintended to invoke the provisions of 35 U.S.C. 112, Paragraph 6.

Please note, if used, the labels left, right, front, back, top, bottom,forward, reverse, clockwise and counter clockwise have been used forconvenience purposes only and are not intended to imply any particularfixed direction. Instead, they are used to reflect relative locationsand/or directions between various portions of an object.

I. DEFINITIONS

As used herein, the term “NASICON,” unless otherwise specified refers tosodium (Na) super ionic conductors which are often characterized by thechemical formula Na_(1+x)Zr₂Si_(x)P_(3−x)O₁₂, 0<x<3, optionally whereinNa, Zr and/or Si are replaced by isovalent elements.

As used herein, the term “LISICON,” unless otherwise specified refers tolithium (Li) super ionic conductors which are often characterized by thechemical formula Li_(2+2x)Zn_(1−x)GeO₄.

As used herein, the phrase “positive electrode” refers to the electrodein a secondary battery towards which positive ions, e.g., Li⁺, flow ormove during discharge of the battery. As used herein, the phrase“negative electrode” refers to the electrode in a secondary battery fromwhere positive ions, e.g., Li⁺, flow or move during discharge of thebattery. In a battery comprised of a Li-metal electrode and a conversionchemistry electrode (i.e., active material; e.g., NiF_(x)), theelectrode having the conversion chemistry materials is referred to asthe positive electrode. In some common usages, cathode is used in placeof positive electrode, and anode is used in place of negative electrode.When a Li-secondary battery is charged, Li ions move from the positiveelectrode (e.g., NiF_(x)) towards the negative electrode (Li-metal).When a Li-secondary battery is discharged, Li ions move towards thepositive electrode (e.g., NiF_(x); i.e., cathode) and from the negativeelectrode (e.g., Li-metal; i.e., anode).

As used herein, the phrase “current collector” refers to a component orlayer in a secondary battery through which electrons conduct, to or froman electrode in order to complete an external circuit, and which are indirect contact with the electrode to or from which the electronsconduct. In some examples, the current collector is a metal (e.g., Al,Cu, or Ni, steel, alloys thereof, or combinations thereof) layer whichis laminated to a positive or negative electrode. During charging anddischarging, electrons move in the opposite direction to the flow of Liions and pass through the current collector when entering or exiting anelectrode.

As used herein, the phrase “at least one member selected from thegroup,” includes a single member from the group, more than one memberfrom the group, or a combination of members from the group. At least onemember selected from the group consisting of A, B, and C includes, forexample, A, only, B, only, or C, only, as well as A and B as well as Aand C as well as B and C as well as A, B, and C or any other allcombinations of A, B, and C.

As used herein, the phrase “slot casting,” refers to a depositionprocess whereby a substrate is coated, or deposited, with a solution,liquid, slurry, or the like by flowing the solution, liquid, slurry, orthe like, through a slot or mold of fixed dimensions that is placedadjacent to, in contact with, or onto the substrate onto which thedeposition or coating occurs. In some examples, slot casting includes aslot opening of about 1 to 100 μm.

As used herein, the phrase “dip casting” or “dip coating” refers to adeposition process whereby substrate is coated, or deposited, with asolution, liquid, slurry, or the like, by moving the substrate into andout of the solution, liquid, slurry, or the like, often in a verticalfashion.

As used herein, the term “laminating” refers to the process ofsequentially depositing a layer of one precursor specie, e.g., a lithiumprecursor specie, onto a deposition substrate and then subsequentlydepositing an additional layer onto an already deposited layer using asecond precursor specie, e.g., a transition metal precursor specie. Thislaminating process can be repeated to build up several layers ofdeposited vapor phases. As used herein, the term “laminating” alsorefers to the process whereby a layer comprising an electrode, e.g.,positive electrode or cathode active material comprising layer, iscontacted to a layer comprising another material, e.g., garnetelectrolyte. The laminating process may include a reaction or use of abinder which adheres of physically maintains the contact between thelayers which are laminated.

As used herein, the phrase “solid state catholyte,” or the term“catholyte” refers to an ion conductor that is intimately mixed with, orsurrounded by, a cathode (i.e., positive electrode) active material(e.g., a metal fluoride optionally including lithium).

As used herein, the term “electrolyte,” refers to an ionicallyconductive and electrically insulating material. Electrolytes are usefulfor electrically insulating the positive and negative electrodes of asecondary battery while allowing for the conduction of ions, e.g., Li⁺,through the electrolyte.

As used herein, the term “anolyte,” refers to an ionically conductivematerial that is mixed with, or layered upon, or laminated to, an anodematerial or anode current collector.

As used herein, the phrase “green film” refers to an unsintered filmincluding at least one member selected from garnet materials, precursorsto garnet materials, binder, solvent, carbon, dispersant, orcombinations thereof.

As used herein, the phrase “evaporating the cathode current collector,”refers to a process of providing or delivering a metal, such as, but notlimited to, copper, nickel, aluminum, or an combination thereof, invapor or atomized form such that the metal contacts and forms anadhering layer to the cathode, catholyte, or combinations thereof or tothe anode, anolyte, or combinations thereof. This process results in theformation of a metal layer on a cathode or anode such that the metallayer and the cathode or anode are in electrical communication.

As used herein the term “making,” refers to the process or method offorming or causing to form the object that is made. For example, makingan energy storage electrode includes the process, process steps, ormethod of causing the electrode of an energy storage device to beformed. The end result of the steps constituting the making of theenergy storage electrode is the production of a material that isfunctional as an electrode.

As used herein the phrase “energy storage electrode,” refers to, forexample, an electrode that is suitable for use in an energy storagedevice, e.g., a lithium rechargeable battery or Li-secondary battery. Asused herein, such an electrode is capable of conducting electrons and Liions as necessary for the charging and discharging of a rechargeablebattery.

As used herein, the phrase “providing” refers to the provision of,generation or, presentation of, or delivery of that which is provided.

As used herein the phrase “providing an unsintered thin film,” refers tothe provision of, generation or, presentation of, or delivery of anunsintered thin film. For example, providing an unsintered thin filmrefers to the process of making an unsintered thin film available, ordelivering an unsintered thin film, such that the unsintered thin filmcan be used as set forth in a method described herein.

As used herein the phrase “unsintered thin film,” refers to a thin film,including the components and materials described herein, but which isnot sintered by a sintering method set forth herein. Thin refers, forexample, to a film that has an average thickness dimensions of about 10nm to about 100 μm. In some examples, thin refers to a film that is lessthan about 1 μm, 10 μm or 50 μm in thickness.

As used herein, the phrase “lithium stuffed garnet” refers to oxidesthat are characterized by a crystal structure related to a garnetcrystal structure. Lithium-stuffed garnets include compounds having theformula Li_(A)La_(B)M′_(c)M″_(D)Zr_(E)O_(F),Li_(A)La_(B)M′_(C)M″_(D)Zr_(E)O_(F), orLi_(A)La_(B)M′_(C)M″_(D)Zr_(E)O_(F), wherein 4<A<8.5, 1.5<B<4, 0≦C≦2,0≦D≦2; 0≦E<2, 10<F<13, and M′ and M″ are each, independently in eachinstance selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta,or Li_(a)La_(b)Zr_(c)Al_(d)Me″_(e)O_(f), wherein 5<a<7.7; 2<b<4;0<c≦2.5; 0≦d<2; 0≦e<2, 10<f<13 and Me″ is a metal selected from Nb, Ta,V, W, Mo, or Sb and as described herein. Garnets, as used herein, alsoinclude those garnets described above that are doped with Al₂O₃.Garnets, as used herein, also include those garnets described above thatare doped so that Al³⁺ substitutes for Li⁺. As used herein,lithium-stuffed garnets, and garnets, generally, include, but are notlimited to, Li_(7.0)La₃(Zr_(t1)+Nb_(t2)+Ta_(t3))O₁₂+0.35Al₂O₃; wherein(t1+t2+t3=subscript 2) so that the La:(Zr/Nb/Ta) ratio is 3:2. Also,garnet used herein includes, but is not limited to,Li_(x)La₃Zr₂O₁₂+yAl₂O₃, wherein x ranges from 5.5 to 9; and y rangesfrom 0 to 1. In some examples x is 7 and y is 1.0. In some examples x is7 and y is 0.35. In some examples x is 7 and y is 0.7. In some examplesx is 7 and y is 0.4. Also, garnets as used herein include, but are notlimited to, Li_(x)La₃Zr₂O₁₂+yAl₂O₃.

As used herein, garnet does not include YAG-garnets (i.e., yttriumaluminum garnets, or, e.g., Y₃Al₅O₂). As used herein, garnet does notinclude silicate-based garnets such as pyrope, almandine, spessartine,grossular, hessonite, or cinnamon-stone, tsavorite, uvarovite andandradite and the solid solutions pyrope-almandine-spessarite anduvarovite-grossular-andradite. Garnets herein do not includenesosilicates having the general formula X₃Y₂(SiO₄)₃ wherein X is Ca,Mg, Fe, and, or, Mn; and Y is Al, Fe, and, or, Cr.

As used herein, the phrase “garnet precursor chemicals” or “chemicalprecursor to a Garnet-type electrolyte” refers to chemicals which reactto form a lithium stuffed garnet material described herein. Thesechemical precursors include, but are not limited to lithium hydroxide(e.g., LiOH), lithium oxide (e.g., Li₂O), lithium carbonate (e.g.,LiCO₃), zirconium oxide (e.g., ZrO₂), lanthanum oxide (e.g., La₂O₃),aluminum oxide (e.g., Al₂O₃), aluminum (e.g., Al), aluminum nitrate(e.g., AlNO₃), aluminum nitrate nonahydrate, niobium oxide (e.g.,Nb₂O₅), tantalum oxide (e.g., Ta₂O₅).

As used herein the phrase “garnet-type electrolyte,” refers to anelectrolyte that includes a garnet or lithium stuffed garnet materialdescribed herein as the ionic conductor.

As used herein, the phrase “doped with alumina” means that Al₂O₂ is usedto replace certain components of another material, e.g., a garnet. Alithium stuffed garnet that is doped with Al₂O₃ refers to garnet whereinaluminum (Al) substitutes for an element in the lithium stuffed garnetchemical formula, which may be, for example, Li or Zr.

As used herein, the phrase “aluminum reaction vessel” refers to acontainer or receptacle into which precursor chemicals are placed inorder to conduct a chemical reaction to produce a product, e.g., alithium stuffed garnet material.

As used herein, the phrase “high conductivity,” refers to aconductivity, such as ionic conductivity, that is greater than 10⁻⁵ S/cmat room temperature. In some examples, high conductivity includes aconductivity greater than 10⁻⁵ S/cm at room temperature.

As used herein, the phrase “Zr is partially replaced by a higher valencespecies” refers to the substitution of Zr⁴⁺ with a species that has, forexample, a 5⁺ or 6⁺ charge. For example, if some Nb⁵⁺ can reside in alattice position in a garnet crystal structure where a Zr atom residesand in doing so substitute for Zr⁴⁺, then Zr is partially replaced byNb. This is also referred to as niobium doping.

As used herein, the phrase “subscripts and molar coefficients in theempirical formulas are based on the quantities of raw materialsinitially batched to make the described examples” means the subscripts,(e.g., 7, 3, 2, 12 in Li₇La₃Zr₂O₁₂ and the coefficient 0.35 in0.35Al₂O₃) refer to the respective elemental ratios in the chemicalprecursors (e.g., LiOH, La₂O₃, ZrO₂, Al₂O₃) used to prepare a givenmaterial, (e.g., Li₇La₃Zr₂O₁₂.0.35Al₂O₃).

As used herein, the phrase “electrochemical device” refers to an energystorage device, such as, but not limited to a Li-secondary battery thatoperates or produces electricity or an electrical current by anelectrochemical reaction, e.g., a conversion chemistry reaction such as3Li+FeF₃⇄3LiF+Fe.

As used herein, the phrase “film thickness” refers to the distance, ormedian measured distance, between the top and bottom faces of a film. Asused herein, the top and bottom faces refer to the sides of the filmhaving the largest surface area.

As used herein, the term “grains” refers to domains of material withinthe bulk of a material that have a physical boundary which distinguishesthe grain from the rest of the material. For example, in some materialsboth crystalline and amorphous components of a material, often havingthe same chemical composition, are distinguished from each other by theboundary between the crystalline component and the amorphous component.The approximate diameter of the boundaries of a crystalline component,or of an amorphous component, is referred herein as the grain size.

As used herein, the phrase “do diameter” refers to the median size, in adistribution of sizes, measured by microscopy techniques or otherparticle size analysis techniques, such as, but not limited to, scanningelectron microscopy or dynamic light scattering. D₅₀ includes thecharacteristic dimension at which 50% of the particles are smaller thanthe recited size.

As used herein the phrase “active electrode material,” or “activematerial,” refers to a material that is suitable for use as a Lirechargeable battery and which undergoes a chemical reaction during thecharging and discharging cycles. For examples, and “active cathodematerial,” includes a metal fluoride that converts to a metal andlithium fluoride during the discharge cycle of a Li rechargeablebattery.

As used herein the phrase “active anode material” refers to an anodematerial that is suitable for use in a Li rechargeable battery thatincludes an active cathode material as defined above. In some examples,the active material is Lithium metal. In some of the methods set forthherein, the sintering temperatures are high enough to melt the Lithiummetal used as the active anode material.

As used herein the phrase “conductive additive,” refers to a materialthat is mixed with the cathode active material in order to improve theconductivity of the cathode. Examples includes, but are not limited to,carbon and the various forms of carbon, e.g., ketjen black, VGCF,acetylene black, graphite, graphene, nanotubes, nanofibers, the like,and combinations thereof.

As used herein the term “solvent,” refers to a liquid that is suitablefor dissolving or solvating a component or material described herein.For example, a solvent includes a liquid, e.g., toluene, which issuitable for dissolving a component, e.g., the binder, used in thegarnet sintering process.

As used herein the phrase “removing a solvent,” refers to the processwhereby a solvent is extracted or separated from the components ormaterials set forth herein. Removing a solvent includes, but is notlimited to, evaporating a solvent. Removing a solvent includes, but isnot limited to, using a vacuum or a reduced pressure to drive off asolvent from a mixture, e.g., an unsintered thin film. In some examples,a thin film that includes a binder and a solvent is heated or alsooptionally placed in a vacuum or reduced atmosphere environment in orderto evaporate the solvent to leave the binder, which was solvated, in thethin film after the solvent is removed.

As used herein the phrase “sintering the film,” refers to a processwhereby a thin film, as described herein, is densified (made denser, ormade with a reduced porosity) through the use of heat sintering or fieldassisted sintering. Sintering includes the process of forming a solidmass of material by heat and/or pressure without melting it to the pointof complete liquification.

As used herein the term “FAST,” refers to the acronym for field assistedsintering. In some examples, FAST also refers to Flash Sintering.

As used herein the phrase “applying a D.C. or A.C. electric field,”refers to a process where a power source is electrically connected to amaterial such that the electric field in the material is altered oreffected by the power source and a current passes through the materialand originates from the power source as either a direct current (D.C.)or an alternating current (A.C.).

As used herein the term “binder,” refers to a material that assists inthe adhesion of another material. For example, as used herein, polyvinylbutyral is a binder because it is useful for adhering garnet materials.Other binders include polycarbonates. Other binders may includepolymethylmethacrylates. These examples of binders are not limiting asto the entire scope of binders contemplated here but merely serve asexamples.

As used herein the phrase “casting a film,” refers to the process ofdelivering or transferring a liquid or a slurry into a mold, or onto asubstrate, such that the liquid or the slurry forms, or is formed into,a film. Casting may be done via doctor blade, meyer rod, comma coater,gravure coater, microgravure, reverse comma coater, slot dye, slipand/or tape casting, and other methods known to those skilled in theart.

As used herein the phrase “applying a pressure,” refers to a processwhereby an external device, e.g., a calender, induces a pressure inanother material.

As used herein the term “about,” refers to a qualification of a numberassociated with the word about. About includes, in some examples, arange ±5-10% around the number qualified by the word about. For example,evaporating a solvent at about 80° C. includes evaporating a solvent at79° C., 80° C., or 81° C.

As used herein the phrase “about 1 to about 600 minutes,” refers to therange 0.1 to 1.1 to 540-660 minutes and the minute values therebetween.As used herein the phrase “about 10 μm to about 100 μm” refers to therange 9 μm-11 μm to 90 μm-110 μm and the integer values therebetween.

As used herein the phrase “about 500° C. to about 900° C.,” refers tothe range 450° C.-550° C. to 810° C.-990° C. and the integer temperaturevalues therebetween.

As used herein the phrase “burning the binder or calcining theunsintered film,” refers to the process whereby a film that includes abinder is heated, optionally in an environment that includes anoxidizing specie, e.g., O₂, in order to burn the binder or induce achemical reaction that drives off, or removes, the binder, e.g.,combustion, or which causes a film having a binder to sinter, to becomemore dense or less porous.

As used herein the phrase “composite electrode,” refers to an electrodethat is composed of more than one material. For example, a compositeelectrode may include, but is not limited to, an active cathode materialand a garnet-type electrolyte in intimate mixture or ordered layers orwherein the active material and the electrolyte are interdigitated.

As used herein the phrase “inert setter plates,” refer to plates, whichare normally flat, and which are unreactive with a material that issintered. Inert setter plates can be metallic or ceramic, and,optionally, these setter plates can be porous to provide for thediffusion of gases and vapors therethrough when a sintered material isactually sintered.

As used herein the phrase “operating in a constant voltage amplitudemode,” refers to an electrochemical process wherein the amplitude of aDC or RMS amplitude of an AC voltage applied to a material is held at aconstant value while allowing the current to vary as a function of theresistance, or impedance, of the material.

As used herein the phrase “operating in a constant current amplitudemode,” refers to an electrochemical process wherein a constant DC or RMSamplitude of an AC current flows through a material while allowing theapplied voltage to vary as a function of the resistance, or impedance,of the material.

As used herein the phrase “free-standing thin film,” refers to a filmthat is not adhered or supported by an underlying substrate. In someexamples, free-standing thin film is a film that is self-supporting,which can be mechanically manipulated or moved without need of substrateadhered or fixed thereto.

As used herein the term “porous,” refers to a material that includespores, e.g., nanopores, mesopores, or micropores.

As used herein the term “pyrolysis,” refers to a thermochemicaldecomposition of organic material at elevated temperatures in theabsence of oxygen.

As used herein the term “electroplating,” refers to a process whereby amaterial, e.g., metal, is deposited in conjunction with the use ofelectricity.

As used herein the phrase “average pore diameter dimensions of about 5nm to about 1 μm” refers to a material that has pores wherein the innerdiameter of the pores therein are physically spaced by about 5 nm, fornanopores for example, or about 1 μm, for micropores for example.

As used herein the phrase “polymer is stable at voltages greater thanabout 3.8V,” refers to a polymer that does not undergo a destructivechemical reaction when a voltage of more than 3.8V relative to a Lithiumreference electrode is applied thereto. A destructive chemical reactionas used herein refers to a chemical reaction that degrades thefunctionality of the polymer for which the polymer is used. For example,if a polymer is ionically conductive and useful as a Li-conductor in aLi battery, then a destructive reaction is a reaction that reduces ordegrades the ability of the polymer to conduct Li ions by more than 10%as measured in S/cm units of conductivity over the life of the productin useful operating conditions of temperature and cycling.

As used herein the term “infiltrated,” refers to the state wherein onematerial passes into another material, or when one material is caused tojoin another material. For example, if a porous Garnet is infiltratedwith carbon, this refers to the process whereby carbon is caused to passinto and intimately mix with the porous Garnet.

As used herein the phrase “operating in a ramped voltage,” refers to anelectrical process wherein the applied voltage is gradually orsystematically increased or decreased over a period of time.

As used herein the phrase “operating a ramped power,” refers to aprocess wherein the applied power is gradually or systematicallyincreased or decreased over a period of time.

As used herein the phrase “operating in a ramped current,” refers to anelectrical process wherein the applied current is gradually orsystematically increased or decreased over a period of time.

As used herein, the term “nanostructured,” or “nanodimensioned” refersto a composite material wherein the constituent components are separatedby nanodimensions. For example, a nanodimensioned composite material mayinclude a Li-containing compound, e.g., LiF, and an Fe-containingcompound, e.g., Fe, wherein the domains of Fe and the domains of LiFhave median physical dimensions of about 1-100 nm, or 2-50 nm, or 1-10nm, or 2-5 nm, or 5-15 nm, or 5-20 nm, or the like as measured in a TEMmicrograph by identification of regions of visual contrast of differentnanodomains.

II. GARNET MATERIALS

Disclosed herein are nanostructured lithium stuffed garnet-based powder.Also disclosed herein are also lithium stuffed garnet thin films thathave grains therein less than 10 μm in physical dimensions, e.g., d₅₀grain sizes less than 10 μm. In some examples, these films are less than50 μm in film thickness. In some of these examples, the films which areless than 50 μm in film thickness are several meters to severalkilometers in length. In some examples, the films have a highconductivity, which in some examples is greater than 10⁻⁴ S/cm. In someexamples, the films are strong, have good mechanical integrity, andprevent the ingress of lithium dendrites when used as an electrolyte inlithium secondary batteries. Some of these films are intimately mixedwith cathode active materials and optionally binders, dispersants,solvents, and other electron and ionic conductors. Also set forthherein, are methods of making these example films.

In other examples, set forth herein are a number of lithium stuffedgarnet compositions that are doped with alumina and which possess theunique combination of high ionic conductivity and fine grain size. Insome examples, these compositions are prepared under lower temperaturesand shorter reaction time conditions than were previously known possiblefor lithium stuffed garnets. Also, in some examples, novel sinteringmethods are employed, some of which employ an environment of Argon gasrather than Air to prepare new lithium stuffed garnets. In addition, insome examples, by using finely milled garnet powder, and, or garnetprecursors, and, or, metal powders, unique thin film architectures areprepared as set forth below. The disclosure herein sets forth a numberof novel lithium-stuffed garnet ceramics having aluminum therein, e.g.,as alumina (Al₂O₃), which advantageously and surprisingly have highionic conductivity and small grain size properties.

A. Lithium Stuffed Garnets

i. Electrolytes

In certain examples, the methods set forth herein include a Garnet-typeelectrolyte material selected from Li_(A)La_(B)M′_(c)M″_(D)Zr_(E)O_(F),Li_(A)La_(B)M′_(C)M″_(D)Zr_(E)O_(F),Li_(A)La_(B)M′_(C)M″_(D)Zr_(E)O_(F), wherein 4<A<8.5, 1.5<B<4, 0≦C≦2,0≦D≦2; 0≦E<2, 10<F<14, and M′ and M″ are each, independently in eachinstance selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta,or Li_(a)La_(b)Zr_(c)Al_(d)Me″_(e)O_(f), wherein 5<a<7.7; 2<b<4;0<c≦2.5; 0≦d<2≦d<2; 0≦e<2, 10<f<14 and Me″ is a metal selected from Nb,Ta, V, W, Mo, or Sb.

In certain examples, the methods set forth herein include a Garnet-typeelectrolyte material selected from Li_(A)La_(B)M′_(c)M″_(D)Zr_(E)O_(F),Li_(A)La_(B)M′_(C)M″_(D)Zr_(E)O_(F),Li_(A)La_(B)M′_(c)M″_(D)Zr_(E)O_(F), wherein 4<A<8.5, 1.5<B<4, 0≦C≦2,0≦D≦2; 0≦E<2, 10<F<13, and M′ and M″ are each, independently in eachinstance selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr. Cc, Hf, Rb, or Ta,or Li_(a)La_(b)Zr_(c)Al_(d)Me″_(e)O_(f), wherein 5<a<7.7; 2<b<4;0<c≦2.5; 0≦d<2; 0≦e<2, 10<f<13 and Me″ is a metal selected from Nb, Ta,V, W, Mo, or Sb.

In certain examples, the methods set forth herein include a Garnet-typeelectrolyte selected from Li_(A)La_(B)M′_(C)M″_(D)Zr_(E)O_(F), wherein4<A<8.5, 1.5<B<4, 0≦C≦2, 0≦D≦2; 0≦E<2, 10<F<14, and M′ and M″ are each,independently in each instance selected from Al, Mo, W, Nb, Sb, Ca, Ba,Sr, Ce, Hf. Rb, or Ta.

In certain examples, the methods set forth herein include a Garnet-typeelectrolyte selected from Li_(A)La_(B)M′_(C)M″_(D)Zr_(E)O_(F), wherein4<A<8.5, 1.5<B<4, 0≦C≦2, 0≦D≦2; 0≦E<2, 10<F<3, and M′ and M″ are each,independently in each instance selected from Al, Mo, W, Nb, Sb, Ca, Ba,Sr, Ce, Hf, Rb, or Ta.

In certain examples, the methods set forth herein include a Garnet-typeelectrolyte selected from Li_(a)La_(b)Zr_(c)Al_(d)Me″_(e)O_(f), wherein5<a<7.7; 2<b<4; 0<c≦2.5; 0≦d<2; 0≦e<2, 10<f<14 and Me″ is a metalselected from Nb, Ta, V, W, Mo, or Sb.

In certain examples, the methods set forth herein include a Garnet-typeelectrolyte selected from Li_(a)La_(b)Zr_(c)Al_(d)Me″_(e)O_(F), wherein5<a<7.7; 2<b<4; 0<c≦2.5; 0≦d≦2; 0≦e<2, 10<f<13 and Me″ is a metalselected from Nb, Ta, V, W, Mo, or Sb.

In some embodiments, the garnet material described herein is used as anelectrolyte. In some of these embodiments, the garnet has the formulaLi_(x)La₃Zr₂O₁₂.y½Al₂O₃; wherein 5.0<x<9 and 0.1<y<1.5. In some of theseexamples, the electrolyte is Li_(x)La₃Zr₂O₁₂.0.35Al₂O₃. In other ofthese examples, the electrolyte is Li₇La₃Zr₂O₁₂.0.35Al₂O₃.

In some of the examples wherein the garnet is an electrolyte, the garnetdoes not include any Nb, Ta, W or Mo, which is used herein to mean thatthe concentration of those elements (e.g., Nb, Ta, W, or Mo) is 10 partsper million (ppm) or lower. In some examples, the concentration of thoseelements (e.g., Nb, Ta, W, or Mo) is 1 parts per million (ppm) or lower.In some examples, the concentration of those elements (e.g., Nb, Ta, W,or Mo) is 0.1 parts per million (ppm) or lower.

In some examples, the Lithium stuffed garnet set forth herein can berepresented by the general formula Li_(x)A₃B₂O₁₂, wherein 5<x<7. In someof these examples, A is a large ion occupying an 8-fold coordinatedlattice site. In some of these examples, A is La, Sr, Ba, Ca, or acombination thereof. In some examples, B is a smaller more highlycharged ion occupying an octahedral site. In some of these examples, Bis Zr, Hf, Nb. Ta, Sb, V, or a combination thereof. In certain of theseexamples, the composition is doped with 0.3 to 1 molar amount of Al perLi_(x)A₃B₂O₁₂. In certain of these examples, the composition is dopedwith 0.35 molar amount of Al per Li_(x)A₃B₂O₁₂.

In some examples, the lithium stuffed garnet is Li₇La₃Zr₂O₁₂(LLZ) and isdoped with alumina. In certain examples, the LLZ is doped by addingAl₂O₃ to the reactant precursor mix that is used to make the LLZ. Incertain other examples, the LLZ is doped by the aluminum in an aluminumreaction vessel that contacts the LLZ.

In some examples, the alumina doped LLZ has a high conductivity, e.g.,greater than 10⁻⁴ S/cm at room temperature.

In some examples, a higher conductivity is observed when some of the Zris partially replaced by a higher valence species, e.g., Nb, Ta, Sb, orcombinations thereof. In some examples, the conductivity reaches as highas 10⁻³ S/cm at room temperature.

In some examples, the composition set forth herein is Li_(x)A₃B₂O₁₂doped with 0.35 molar amount of Al per Li_(x)A₃B₂O₁₂. In certain ofthese examples, x is 5. In certain other examples, x is 5.5. In yetother examples, x is 6.0. In some other examples, x is 6.5. In stillother examples, x is 7.0. In some other examples, x is 7.5

In some examples, the garnet-based composition is doped with 0.3, 0.35,0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, or 1molar amount of Al per Li_(x)A₃B₂O₁₂.

In some examples, the garnet-based composition is doped with 0.35 molaramount of AI per Li_(x)A₃B₂O₂.

In the examples, herein, the subscripts and molar coefficients in theempirical formulas are based on the quantities of raw materialsinitially batched to make the described examples.

In some examples, the instant disclosure provides a compositionincluding a lithium stuffed garnet and Al₂O₃. In certain examples, thelithium stuffed garnet is doped with alumina.

In some examples, the lithium-stuffed garnet is characterized by theempirical formula Li_(A)La_(B)M′_(c)M″_(D)Zr_(E)O_(F), wherein 4<A<8.5,1.5<B<4, 0≦C≦2, 0≦D≦2; 0≦E≦2, 10<F≦13, and M′ and M″ are, independentlyin each instance, either absent or are each independently selected fromAl, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta; and wherein the molarratio of Garnet:Al₂O₃ is between 0.05 and 0.7.

In some examples, the instant disclosure provides a compositionincluding a lithium stuffed garnet and Al₂O₃. In certain examples, thelithium stuffed garnet is doped with alumina. In some examples, thelithium-stuffed garnet is characterized by the empirical formulaLi_(A)La_(B)M′_(c)M″_(D)Zr_(E)O_(F), wherein 4<A<8.5, 1.5<B<4, 0≦C≦2,0≦D≦2; 0≦E≦2, 10<F≦13, and M′ and M″ are, independently in eachinstance, either absent or are each independently selected from Al, Mo,W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta; and wherein the molar ratio ofLi:Al is between 0.05 and 0.7.

In some examples, the instant disclosure provides a compositionincluding a lithium stuffed garnet and Al₂O₃. In certain examples, thelithium stuffed garnet is doped with alumina.

In some examples, the lithium-stuffed garnet is characterized by theempirical formula Li_(A)La_(B)M′_(c)M″_(D)Zr_(E)O_(F), wherein 2<A<10,2<1B<6, 0≦C≦2, 0≦D=2; 0<E<3, 8<F<14, and M′ and M″ are, independently ineach instance, either absent or are each independently selected from Al,Mo, W, Nb, Sb, Ca, Ba. Sr, Ce, Hf, Rb, or Ta; and wherein the molarratio of Garnet:Al₂O₃ is between 0.01 and 2.

In some examples, the instant disclosure provides a compositionincluding a lithium stuffed garnet and Al₂O₃. In certain examples, thelithium stuffed garnet is doped with alumina. In some examples, thelithium-stuffed garnet is characterized by the empirical formulaLi_(A)La_(B)M′_(c)M″_(D)Zr_(E)O_(F), wherein 2<A<0, 2<B<6, 0≦C≦2, 0≦D≦2;0≦E≦3, 8<F≦14, and M′ and M″ are, independently in each instance, eitherabsent or are each independently selected from Al, Mo, W, Nb, Sb, Ca,Ba, Sr, Ce, Hf, Rb, or Ta; and wherein the molar ratio of Li:Al isbetween 0.01 and 2.

in some examples, the lithium stuffed garnet isLi_(A)La_(B)Zr_(C)M′_(D)M″_(E)O₁₂ and 5<A<7.7, 2<B<4, 0<C<2.5, M′comprises a metal dopant selected from a material including Al and0<D<2, M″ comprises a metal dopant selected from a material includingNb, Ta, V, W, Mo, Sb, and wherein 0<e<2. In some examples, the lithiumstuffed garnet is a lithium stuffed garnet set forth in U.S. ProvisionalPatent Application No. 61/887,451, entitled METHOD AND SYSTEM FORFORMING GARNET MATERIALS WITH SINTERING PROCESS, filed Oct. 7, 2013, theentire contents of which are herein incorporated by reference in itsentirety for all purposes.

In some of the examples above, A is 6. In some other examples, A is 6.5.In other examples, A is 7.0. In certain other examples, A is 7.5. In yetother examples, A is 8.0.

In some of the examples above, B is 2. In some other examples, B is 2.5.In other examples, B is 3.0. In certain other examples, B is 3.5. In yetother examples, B is 3.5. In yet other examples, B is 4.0.

In some of the examples above, C is 0.5. In other examples C is 0.6. Insome other examples, C is 0.7. In some other examples C is 0.8. Incertain other examples C is 0.9. In other examples C is 1.0. In yetother examples, C is 1.1. In certain examples, C is 1.2. In otherexamples C is 1.3. In some other examples, C is 1.4. In some otherexamples C is 1.5. In certain other examples C is 1.6. In other examplesC is 1.7. In yet other examples, C is 1.8. In certain examples, C is1.9. In yet other examples, C is 2.0. In other examples C is 2.1. Insome other examples, C is 2.2. In some other examples C is 2.3. Incertain other examples C is 2.4. In other examples C is 2.5. In yetother examples, C is 2.6. In certain examples, C is 2.7. In yet otherexamples, C is 2.8. In other examples C is 2.9. In some other examples,C is 3.0.

In some of the examples above, D is 0.5. In other examples D is 0.6. Insome other examples, D is 0.7. In some other examples I) is 0.8. Incertain other examples D is 0.9. In other examples D is 1.0. In yetother examples, D is 1.1. In certain examples, D is 1.2. In otherexamples D is 1.3. In some other examples, D is 1.4. In some otherexamples D is 1.5. In certain other examples D is 1.6. In other examplesD is 1.7. In yet other examples, D is 1.8. In certain examples, D is1.9. In yet other examples, D is 2.0. In other examples D is 2.1. Insome other examples, D is 2.2. In some other examples D is 2.3. Incertain other examples D is 2.4. In other examples D is 2.5. In yetother examples, D is 2.6. In certain examples, D is 2.7. In yet otherexamples, D is 2.8. In other examples D is 2.9. In some other examples,D is 3.0.

In some of the examples above, E is 0.5. In other examples E is 0.6. Insome other examples, E is 0.7. In some other examples E is 0.8. Incertain other examples E is 0.9. In other examples E is 1.0. In yetother examples, E is 1.1. In certain examples, E is 1.2. In otherexamples E is 1.3. In some other examples, E is 1.4. In some otherexamples E is 1.5. In certain other examples E is 1.6. In other examplesE is 1.7. In yet other examples, E is 1.8. In certain examples, E is1.9. In yet other examples, E is 2.0. In other examples E is 2.1. Insome other examples, E is 2.2. In some other examples E is 2.3. Incertain other examples E is 2.4. In other examples E is 2.5. In yetother examples, E is 2.6. In certain examples, E is 2.7. In yet otherexamples, E is 2.8. In other examples E is 2.9. In some other examples,E is 3.0.

In some of the examples above, F is 11.1. In other examples F is 11.2.In some other examples, F is 11.3. In some other examples F is 11.4. Incertain other examples F is 11.5. In other examples F is 11.6. In yetother examples, F is 11.7. In certain examples, F is 11.8. In otherexamples F is 11.9. In some other examples, F is 12. In some otherexamples F is 12.1. In certain other examples F is 12.2. In otherexamples F is 12.3. In yet other examples, F is 12.3. In certainexamples, F is 12.4. In yet other examples, F is 12.5. In other examplesF is 12.6. In some other examples, F is 12.7. In some other examples Fis 12.8. In certain other examples E is 12.9. In other examples F is 13.

In some examples, provided herein is a composition characterized by theempirical formula Li_(x)La₃Zr₂O₁₂.y½Al₂O₃; wherein 5.0<x<9 and 0,1<y<1.5. In some examples, x is 5. In other examples, x is 5.5. In someexamples, x is 6. In some examples, x is 6.5. In other examples, x is 7.In some examples, x is 7.5. In other examples x is 8. In some examples,y is 0.3. In some examples, y is 0.35. In other examples, y is 0.4. Insome examples, y is 0.45. In some examples, y is 0.5. In other examples,y is 0.55. In some examples, y is 0.6. In other examples y is 0.7. Insome examples, y is 0.75. In other examples, y is 0.8. In some examples,y is 0.85. In other examples y is 0.9. In some examples, y is 0.95. Inother examples, y is 1.0

In some examples, provided herein is a composition characterized by theempirical formula Li_(7.0)La₃(Zr_(t1)+Nb_(t2)+Ta_(t3))O₁₂+0.35Al₂O₃. Inthis formula, t1+t2+t3=subscript 2 so that the molar ratio of La to thecombined amount of (Zr+Nb+Ta) is 3.2.

In some examples, provided herein is a composition is characterized bythe empirical formula Li₇La₃Zr₂O₁₂.0.35Al₂O₃.

In some of the above examples, A is 5, 6, 7, or 8. In certain examples,wherein A is 7.

In some of the above examples, M′ is Nb and M″ is Ta.

In some of the above examples, E is 1, 1.5, or 2. In certain examples, Eis 2.

In some of the above examples, C and D are 0.

In some examples, provided herein is a composition wherein the molarratio of Garnet:Al₂O₃ is between 0.1 and 0.65. In some examples, theLi:Al ratio is between 7:0.2 to 7:1.3. In some examples, the Li:Al ratiois between 7:0.3 to 7:1.2. In some examples, the Li:Al ratio is between7:0.3 to 7:1.1. In some examples, the Li:Al ratio is between 7:0.4 to7:1.0. In some examples, the Li:Al ratio is between 7:0.5 to 7:0.9. Insome examples, the Li:Al ratio is between 7:0.6 to 7:0.8. In someexamples, the Li:Al ratio is about 7:0.7. In some examples, the Li:Alratio is 7:0.7.

In some examples, provided herein is a composition wherein the molarratio of Garnet:Al₂O₃ is between 0.15 and 0.55.

In some examples, provided herein is a composition wherein the molarratio of Garnet:Al₂O₃ is between 0.25 and 0.45.

In some examples, provided herein is a composition wherein the molarratio of Garnet:Al₂O₃ is 0.35.

In some examples, provided herein is a composition wherein the molarratio of Al to garnet is 0.35.

In some examples, provided herein is a composition wherein thelithium-stuffed garnet is characterized by the empirical formulaLi₇La₃Zr₂O₁₂ and is doped with aluminum.

In some examples, the lithium stuffed garnet is Li₇La₃Zr₂O₁₂(LLZ) and isdoped with alumina. In certain examples, the LLZ is doped by addingAl₂O₃ to the reactant precursor mix that is used to make the LLZ. Incertain other examples, the LLZ is doped by the aluminum in an aluminumreaction vessel that contacts the LLZ. When the LLZ is doped withalumina, conductive holes are introduced which increases theconductivity of the lithium stuffed garnet.

In some examples, this increased conductivity is referred to asincreased ionic (e.g., Li⁺) conductivity.

ii. Catholytes

Catholyte materials suitable for use with the components, devices, andmethods set forth herein include, without limitation, a garnet materialselected from Li_(A)La_(B)M′_(c)M″_(D)Zr_(E)O_(F),Li_(A)La_(B)M′_(c)M″_(D)Zr_(E)O_(F),Li_(A)La_(B)M′_(C)M″_(D)Zr_(E)O_(F), wherein 4<A<8.5, 1.5<B<4, 0≦C≦2,0≦D≦2; 0≦E<2, 10<F<14, and M′ and M″ are each, independently in eachinstance selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta,or Li_(a)La_(b)M′_(c)M″_(d)Zr_(e)O_(f), wherein 5<a<7.7; 2<b<4; 0<c≦2.5;0≦d<2; 0≦e<2, 10<f<14 and Me″ is a metal selected from Nb, Ta, V, W, Mo,or Sb. In some embodiments, the garnet material isLi_(A)La_(B)M′_(c)M″_(D)Zr_(E)O_(F). In some other embodiments, thegarnet material is Li_(A)La_(B)M′_(C)M″_(D)Ta_(E)O_(F). In otherembodiments, the garnet material is Li_(A)La_(B)M′_(C)M″_(D)Nb_(E)O_(F).

In the above examples, the subscript value (4<A<8.5, 1.5<B<4, 0≦C≦2,0≦D≦2; 0≦E<2, 10<F<14) characterize the ratio of reactants used to makethe garnet material. Certain deviations from these reactant ratios maybe present in the garnet products. As used herein, precursors to Garnetrefers to the reactants used to produce or to synthesize the Garnet.

In the above examples, the subscript value (e.g., 4<A<8.5, 1.5<B<4,0≦C≦2, 0≦D≦2; 0≦E<2, 10<F≦13) characterize the ratio of reactants usedto make the garnet material. Certain deviations from these reactantratios may be present in the garnet products. As used herein, precursorsto Garnet refers to the reactants used to produce Garnet.

In the above examples, the subscript values may also include 4<A<8.5,1.5<B<4, C<2, 0≦D≦2; 0≦E<2, 10<F<14. In some examples, C is equal to1.99 or less.

In the above examples, the subscript values may also include 4<A<8.5,1.5<B<4, C<2, 0≦D≦2; 0≦E<2, 10<F≦13. In some examples, C is equal to1.99 or less.

In certain embodiments, the garnet is a lithium-stuffed garnet.

In some embodiments, the garnet is characterizedLi_(a)La_(b)Zr_(c)Al_(d)Me″_(e)O_(f), wherein the subscripts arecharacterized by the values noted above.

In some embodiments, the lithium-stuffed garnet is a lithium lanthanumzirconium oxide that is mixed with aluminum oxide. In some of theseexamples, the lithium lanthanum zirconium oxide is characterized by theformula Li_(7.0)La₃Zr₂O₁₂+0.35Al₂O₃, wherein the subscript andcoefficients represent molar ratios that are determined based on thereactants used to make the garnet.

in some embodiments, the ratio of La:Zr is 3:2. In some other examples,the garnet is Li_(7.0)La₃(Zr_(t1)+Nb_(t2)+Ta_(t3))O₁₂+0.35Al₂O₃; wherein(t1+t2+t3=subscript 2) so that the La:(Zr/Nb/Ta) ratio is 3:2.

In some examples, the garnet is Li_(x)La₃Zr₂O₁₂+yAl₂O₃, wherein x rangesfrom 5.5 to 9; and y ranges from 0 to 1. In some examples x is 7 and yis 0.35.

The catholytes set forth herein include, in some embodiments, ahierarchical structure with a lithium conducting garnet scaffold filledwith carbon electron conductive additive, lithium conductive polymerbinder, and active material. The active material loading can be greaterthan 50 volume percent to enable high energy density. In some examples,the garnet is sintered and retains >70% porosity to allow for the volumeof the other components. The disclosures herein overcomes severalproblems associated with the assembly of a solid energy storage device,for example, but not limited to, sintering composite electrodes havingwell developed contact points between particles and reducedparticle-particle electrical resistance, which permits higher currentflow without a significant voltage drop: also preparing methods formaking entire device (electrodes, and electrolyte) in one step; alsopreparation methods for making solid state energy storage devices whicheliminate the need to use a flammable liquid electrolyte, which is asafety hazard in some instances; and methods for FAST sintering films toreduce the process time and expense of making electrochemical devices;and methods for making FAST sintering and densifying components ofelectrode composites without significant interdiffusion or detrimentalchemical reaction.

iii. Composites

In some embodiments, disclosed herein is a composite electrochemicaldevice prepared by a method set forth herein. In some examples, thedevice includes at least one layer including a member selected from thegroup consisting of an active electrode material, an electrolyte, aconductive additive, and combinations thereof; and a least one layercomprising a Garnet-type electrolyte. In some examples, the compositehas the structure shown in FIG. 26 or in FIG. 27.

In some embodiments, the device further includes at least one layercomprising an active anode material. Active anode materials include, butare not limited to, carbon, silicon, silicon oxide, tin, alloys thereof,and combinations thereof.

In some embodiments, disclosed herein is a layered material for anelectrochemical device, including at least one layer comprising an anodeand an anode current collector; at least one layer including a garnetsolid state electrolyte (SSE) in contact with the anode; at least onelayer including a porous garnet in contact with the garnet SSE; whereinthe porous garnet is optionally infiltrated with at least one memberselected from the group consisting of carbon, a lithium conductingpolymer, an active cathode material, and combinations thereof; and atleast one layer comprising an aluminum cathode current collector incontact with the porous Garnet, wherein the porous Garnet layer is atleast 70% porous by volume; wherein the Garnet is a material selectedfrom Li_(A)La_(B)M′_(c)M″_(D)Zr_(E)O_(F),Li_(A)La_(B)M′_(C)M″_(D)Ta_(E)O_(F),Li_(A)La_(B)M′_(C)M′_(C)M″_(D)Nb_(E)O_(F), wherein 4<A<8.5, 1.5<B<4,0≦C≦2, 0≦D≦2; 0≦E<2, 10<F<14, and M′ and M″ are each, independently ineach instance selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb,or Ta, or Li_(a)La_(b)Zr_(c)Al_(d)Me″_(e)O_(f), wherein 5<a<7.7; 2<b<4;0<c≦2.5; 0≦d<2; 0≦e<2, 10<f≦13 and Me″ is a metal selected from Nb, Ta,V. W, Mo, or Sb; and wherein the active electrode material is a cathodematerial selected from NCA (lithium nickel cobalt aluminum oxide), LMNO(lithium manganese nickel oxide), NMC (lithium nickel manganese cobaltoxide), LCO (lithium cobalt oxide, i.e., LiCoO₂), nickel fluoride(NiF_(x), wherein x is from 0 to 2.5), copper fluoride (CuF_(y), whereiny is from 0 to 2.5), or FeF_(z) (wherein z is selected from 0 to 3.5).In some examples, the layered structure is substantially as shown inFIG. 25.

In certain embodiments, the two sides of the layer comprising the anodeand anode current collector are each independently in contact with agarnet SSE layer and each garnet SSE layer is independently in contactwith a porous Garnet layer.

b. Powders

i. Nanocrystalline

In some examples, the lithium stuffed garnet powders set forth hereinare nanodimensioned or nanostructured. As such, these powders comprisecrystalline domains of lithium stuffed garnet wherein the mediancrystalline domain diameter is about 0.5 nm to about 10 μm in physicaldimensions (e.g., diameter). In some examples, the crystalline domainsare about 0.5 nm in diameter. In some other examples, the crystallinedomains are about 1 nm in diameter. In other examples, the crystallinedomains are about 1.5 nm in diameter. In yet other examples, thecrystalline domains are about 2 nm in diameter. In still other examples,the crystalline domains are about 2.5 nm in diameter. In some examples,the crystalline domains are about 3.0 nm in diameter. In yet otherexamples, the crystalline domains are about 3.5 nm in diameter. In otherexamples, the crystalline domains are about 4.0 nm in diameter. In someexamples, the crystalline domains are about 5 nm in diameter. In someother examples, the crystalline domains are about 5.5 nm in diameter. Inother examples, the crystalline domains are about 6.0 nm in diameter. Inyet other examples, the crystalline domains are about 6.5 nm indiameter. In still other examples, the crystalline domains are about 7.0nm in diameter. In some examples, the crystalline domains are about 7.5nm in diameter. In yet other examples, the crystalline domains are about8.0 nm in diameter. In other examples, the crystalline domains are about8.5 nm in diameter. In some examples, the crystalline domains are about8.5 nm in diameter. In some other examples, the crystalline domains areabout 9 nm in diameter. In other examples, the crystalline domains areabout 9.5 nm in diameter. In yet other examples, the crystalline domainsare about 10 nm in diameter. In still other examples, the crystallinedomains are about 10.5 nm in diameter. In some examples, the crystallinedomains are about 11.0 nm in diameter. In yet other examples, thecrystalline domains are about 11.5 nm in diameter. In other examples,the crystalline domains are about 12.0 nm in diameter. In some examples,the crystalline domains are about 12.5 nm in diameter. In some otherexamples, the crystalline domains are about 13.5 nm in diameter. Inother examples, the crystalline domains are about 14.0 nm in diameter.In yet other examples, the crystalline domains are about 14.5 nm indiameter. In still other examples, the crystalline domains are about15.0 nm in diameter. In some examples, the crystalline domains are about15.5 nm in diameter. In yet other examples, the crystalline domains areabout 16.0 nm in diameter. In other examples, the crystalline domainsare about 16.5 nm in diameter. In some examples, the crystalline domainsare about 17 nm in diameter. In some other examples, the crystallinedomains are about 17.5 nm in diameter. In other examples, thecrystalline domains are about 18 nm in diameter. In yet other examples,the crystalline domains are about 18.5 nm in diameter. In still otherexamples, the crystalline domains are about 19 nm in diameter. In someexamples, the crystalline domains are about 19.5 nm in diameter. In yetother examples, the crystalline domains are about 20 nm in diameter. Inother examples, the crystalline domains are about 20.5 nm in diameter.In some examples, the crystalline domains are about 21 nm in diameter.In some other examples, the crystalline domains are about 21.5 nm indiameter. In other examples, the crystalline domains are about 22.0 nmin diameter. In yet other examples, the crystalline domains are about22.5 nm in diameter. In still other examples, the crystalline domainsare about 23.0 nm in diameter. In some examples, the crystalline domainsare about 23.5 nm in diameter. In yet other examples, the crystallinedomains are about 24.0 nm in diameter. In other examples, thecrystalline domains are about 24.5 nm in diameter. In some examples, thecrystalline domains are about 25.5 nm in diameter. In some otherexamples, the crystalline domains are about 26 nm in diameter. In otherexamples, the crystalline domains are about 26.5 nm in diameter. In yetother examples, the crystalline domains are about 27 nm in diameter. Instill other examples, the crystalline domains are about 27.5 nm indiameter. In some examples, the crystalline domains are about 28.0 nm indiameter. In yet other examples, the crystalline domains are about 28.5nm in diameter. In other examples, the crystalline domains are about29.0 nm in diameter. In some examples, the crystalline domains are about29.5 nm in diameter. In some other examples, the crystalline domains areabout 30 nm in diameter. In other examples, the crystalline domains areabout 30.5 nm in diameter. In yet other examples, the crystallinedomains are about 31 nm in diameter. In still other examples, thecrystalline domains are about 32 nm in diameter. In some examples, thecrystalline domains are about 33 nm in diameter. In yet other examples,the crystalline domains are about 34 nm in diameter. In other examples,the crystalline domains are about 35 nm in diameter. In some examples,the crystalline domains are about 40 nm in diameter. In some otherexamples, the crystalline domains are about 45 nm in diameter. In otherexamples, the crystalline domains are about 50 nm in diameter. In yetother examples, the crystalline domains are about 55 nm in diameter. Instill other examples, the crystalline domains are about 60 nm indiameter. In some examples, the crystalline domains are about 65 nm indiameter. In yet other examples, the crystalline domains are about 70 nmin diameter. In other examples, the crystalline domains are about 80 nmin diameter. In some examples, the crystalline domains are about 85 nmin diameter. In some other examples, the crystalline domains are about90 nm in diameter. In other examples, the crystalline domains are about100 nm in diameter. In yet other examples, the crystalline domains areabout 125 nm in diameter. In still other examples, the crystallinedomains are about 150 nm in diameter. In some examples, the crystallinedomains are about 200 nm in diameter. In yet other examples, thecrystalline domains are about 250 nm in diameter. In other examples, thecrystalline domains are about 300 nm in diameter. In some examples, thecrystalline domains are about 350 nm in diameter. In some otherexamples, the crystalline domains are about 400 nm in diameter. In otherexamples, the crystalline domains are about 450 nm in diameter. In yetother examples, the crystalline domains are about 500 nm in diameter. Instill other examples, the crystalline domains are about 550 nm indiameter. In some examples, the crystalline domains are about 600 nm indiameter. In yet other examples, the crystalline domains are about 650nm in diameter. In other examples, the crystalline domains are about 700nm in diameter. In some examples, the crystalline domains are about 750nm in diameter. In some other examples, the crystalline domains areabout 800 nm in diameter. In other examples, the crystalline domains areabout 850 nm in diameter. In yet other examples, the crystalline domainsare about 900 nm in diameter. In still other examples, the crystallinedomains are about 950 nm in diameter. In some examples, the crystallinedomains are about 1000 nm in diameter.

ii. Fine Grained

Grain sizes, as used herein and unless otherwise specified, are measuredby either microscopy, e.g., transmission electron microscopy or scanningelectron microscopy, or by x-ray diffraction methods.

In some examples, provided herein is a film having grains with a d₅₀diameter less than 10 μm. In certain examples, the film has grainshaving a ds diameter less than 9 μm. In other examples, the grainshaving a d₅₀ diameter less than 8 μm. In some examples, the grains havea d₅₀ diameter less than 7 μm. In certain examples, the film has grainshaving a d₅₀ diameter less than 6 μm. In other examples, the film hasgrains having a d₅₀ diameter less than 5 μm. In some examples, the filmhas grains having a d₅₀ diameter less than 4 sun. In other examples, thefilm has grains having a d₅₀ diameter less than 3 μm. In certainexamples, the film has grains having a d₅₀ diameter less than 2 μm. Inother examples, the film has grains having a d₅₀ diameter less than 1μm.

As used herein, the fine grains in the films set forth herein have d₅₀diameters of between 10 nm and 10 μm. In some examples, the fine grainsin the films set forth herein have d₅₀ diameters of between 100 nm and10 μm.

In some examples, the films set forth herein have a Young's Modulus ofabout 130-150 GPa. In some other examples, the films set forth hereinhave a Vicker's hardness of about 5-7 GPa.

In some examples, the films set forth herein have a porosity less than20%. In other examples, the films set forth herein have a porosity lessthan 10%. In yet other examples, the films set forth herein have aporosity less than 5%. In still other examples, the films set forthherein have a porosity less than 3%. Porosity is measured, in someexamples, by pycnometry or mercury porosimetry.

c. Films

i. Uncalcined

Set forth herein are films and powders that include garnet precursorsoptionally with calcined garnets. Prior to heating these films andpowders, or prior to a sufficient lapse in time for the precursors toreact in order to form a lithium stuffed garnet, these films and powdersare uncalcined. In some examples, slurries of garnet precursors, setforth below, are layered, deposited, or laminated to calcined films oflithium stuffed garnets in order to build up several layers of lithiumstuffed garnets. In some examples, slurries of garnet precursors, setforth below, are layered, deposited, or laminated to calcined films oflithium stuffed garnets in order to infiltrate vacant or porous spacewithin calcined lithium stuffed garnets.

In some examples, set forth herein are thin and free standing garnetfilms including garnet precursors or optionally calcined garnet. In someexamples, these films also include at least one member selected abinder, a solvent, a dispersant, or combinations thereof. In someexamples, the garnet solid loading is at least 30% by weight (w/w). Insome examples, the film thickness is less than 100 μm.

In certain examples, the dispersant is fish oil, Mehaden Blown Fish Oil,phosphate esters, Rhodaline™, Rhodoline 4160, phospholan-131 ™, BYK™22124, BYK-22146™, Hypermer KD1™, Hypermer KD6™ and Hypermer KD7™.

In some examples, the films include a substrate adhered thereto. Incertain examples, the substrate is a polymer, a metal foil, or a metalpowder. In some of these examples, the substrate is a metal foil. Insome examples, the substrate is a metal powder. In some of theseexamples, the metal is selected from Ni, Cu, Al, steel, alloys, orcombinations thereof.

The film of claim 1, wherein the solid loading is at least 35% w/w.

In some examples, the films have a solid loading of at least 40% w/w. Insome examples, the films have a solid loading of at least 45% w/w. Insome examples, the films have a solid loading of at least 50% w/w. Inothers examples, the solid loading is at least 55% w/w.

In some other examples, the solid loading is at least 60% w/w. In someexamples, the solid loading is at least 65% w/w. In some other examples,the solid loading is at least 70% w/w. In certain other examples, thesolid loading is at least 75% w/w. In some examples, the solid loadingis at least 80% w/w.

In some examples, the uncalcined films have a film thickness less than75 μm and greater than 10 nm. In some examples, the uncalcined filmshave a thickness less than 50 μm and greater than 10 nm. In someexamples, the uncalcined films have a particles which are less than 1 μmat the particles maximum physical dimension. In some examples, theuncalcined films have a median grain size of between 0.1 μm to 10 μm. Insome examples, the uncalcined films is not adhered to any substrate.

In some examples, set forth herein are thin and free standing garnetfilms including garnet precursors or optionally calcined garnet. In someexamples, these films also include at least one member selected abinder, a solvent, a dispersant, or combinations thereof. In someexamples, the garnet solid loading is at least 30% by volume (v/v). Insome examples, the film thickness is less than 100 μm.

In some examples, the films have a solid loading of at least 40% v/v. Insome examples, the films have a solid loading of at least 45% v/v. Insome examples, the films have a solid loading of at least 50% v/v. Inothers examples, the solid loading is at least 55% v/v. In some otherexamples, the solid loading is at least 60% v/v. In some examples, thesolid loading is at least 65% vv. In some other examples, the solidloading is at least 70% vv. In certain other examples, the solid loadingis at least 75% v/v. In some examples, the solid loading is at least 80%v/v.

a. Calcined

The uncalcined films set forth herein may be calcined by heating thefilms to about 200° C. to 1200° C. for about 20 minutes to 10 hours oruntil crystallization occurs.

ii. Unsintered

In some examples, the garnet-based films are unsintered, referred as to“green” films and up to kilometers in length.

In an embodiment, the disclosure sets forth herein a method of making anenergy storage electrode, including providing an unsintered thin film;wherein the unsintered thin film comprises at least one member selectedfrom the group consisting of a Garnet-type electrolyte, an activeelectrode material, a conductive additive, a solvent, a binder, andcombinations thereof; removing the solvent, if present in the unsinteredthin film; optionally laminating the film to a surface; removing thebinder, if present in the film; sintering the film, wherein sinteringcomprises heat sintering or field assisted sintering (FAST); whereinheat sintering includes heating the film in the range from about 700° C.to about 1200° C. for about 1 to about 600 minutes and in atmospherehaving an oxygen partial pressure between 1e-1 atm to 1e-15 atm; andwherein FAST sintering includes heating the film in the range from about500° C. to about 900° C. and applying a D.C. or A.C. electric field tothe thin film.

In some of the methods disclosed herein, the unsintered thin film has athickness from about 10 μm to about 100 μm. In some other of the methodsdisclosed herein, the unsintered thin film has a thickness from about 20μm to about 100 μm. In certain of the methods disclosed herein, theunsintered thin film has a thickness from about 30 μm to about 100 μm.In certain other of the methods disclosed herein, the unsintered thinfilm has a thickness from about 40 μm to about 100 μm. In yet othermethods disclosed herein, the unsintered thin film has a thickness fromabout 50 μm to about 100 μm. In still other methods disclosed herein,the unsintered thin film has a thickness from about 60 μm to about 100μm. In yet some other methods disclosed herein, the unsintered thin filmhas a thickness from about 70 μm to about 100 μm. In some of the methodsdisclosed herein, the unsintered thin film has a thickness from about 80μm to about 100 μm. In some other of the methods disclosed herein, theunsintered thin film has a thickness from about 90 μm to about 100 μm.

In some of the methods disclosed herein, the unsintered thin film has athickness from about 10 μm to about 90 μm. In some other of the methodsdisclosed herein, the unsintered thin film has a thickness from about 20μm to about 80 μm. In certain of the methods disclosed herein, theunsintered thin film has a thickness from about 30 μm to about 70 μm. Incertain other of the methods disclosed herein, the unsintered thin filmhas a thickness from about 40 μm to about 60 μm. In yet other methodsdisclosed herein, the unsintered thin film has a thickness from about 50μm to about 90 μm. In still other methods disclosed herein, theunsintered thin film has a thickness from about 60 μm to about 90 μm. Inyet some other methods disclosed herein, the unsintered thin film has athickness from about 70 μm to about 90 μm. In some of the methodsdisclosed herein, the unsintered thin film has a thickness from about 80μm to about 90 μm. In some other of the methods disclosed herein, theunsintered thin film has a thickness from about 30 μm to about 60 μm.

In some examples, the unsintered films are about 50 percent larger byvolume than the sintered films. In some examples, the sintered filmshave a thickness of about 1-150 μm. In some of these examples thesintered films has a thickness of about 1 μm. In some other examples thesintered films has a thickness of about 2 μm. In certain examples thesintered films has a thickness of about 3 μm. In certain other examplesthe sintered films has a thickness of about 4 μm. In some other examplesthe sintered films has a thickness of about 5 μm. In some examples thesintered films has a thickness of about 6 μm. In some of these examplesthe sintered films has a thickness of about 7 μm. In some examples thesintered films has a thickness of about 8 μm. In some other examples thesintered films has a thickness of about 9 μm. In certain examples thesintered films has a thickness of about 10 μm.

In some examples, the sintering reduces the thickness of the film byabout 50, about 40, about 30, about 20, about 10, or about 5% withoutreducing the length of the film by more than about 1, 2, 3, 4, 5, 6, 7,8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or25%. As used herein, the thickness refers to the average thickness inthe z-direction (as shown in FIG. 23. As used herein, the length refersto the average length in the x-direction or in the y-direction (as shownin FIG. 23). In some examples, the sintering described herein reducesthe thickness of the film in the z-direction (as shown in FIG. 23)proportionally more than in the x or y directions. In some examples, thesintering primarily reduces the film thickness in the z-directionproportionally more so than in either the x- or in the y-direction. Insome examples, the sintering reduces the thickness of the film in thei-direction (as shown in FIG. 23) proportionally substantially more thanthe sintering reduces the length of the film in the x- or in they-direction. As used in this paragraph, substantially more includes, butis not limited to, at least 50%, at least 60%, at least 70%, at least80%, at least 90%, or at least 100%.

iii. Sintered

In some of these examples the sintered films has a thickness of about 10nm. In some other examples the sintered films has a thickness of about11 nm. In certain examples the sintered films has a thickness of about12 nm. In certain other examples the sintered films has a thickness ofabout 13 nm. In some other examples the sintered films has a thicknessof about 14 nm. In some examples the sintered films has a thickness ofabout 15 nm. In some of these examples the sintered films has athickness of about 16 nm. In some examples the sintered films has athickness of about 17 nm. In some other examples the sintered films hasa thickness of about 18 nm. In certain examples the sintered films has athickness of about 19 nm. In some of these examples the sintered filmshas a thickness of about 20 nm. In some other examples the sinteredfilms has a thickness of about 21 nm. In certain examples the sinteredfilms has a thickness of about 22 nm. In certain other examples thesintered films has a thickness of about 23 nm. In some other examplesthe sintered films has a thickness of about 24 nm. In some examples, thesintered film has a thickness of about 25 nm. In some examples thesintered films has a thickness of about 26 nm. In some of these examplesthe sintered films has a thickness of about 27 nm. In some examples thesintered films has a thickness of about 28 nm. In some other examplesthe sintered films has a thickness of about 29 nm. In certain examplesthe sintered films has a thickness of about 30 nm. In some of theseexamples the sintered films has a thickness of about 31 nm. In someother examples the sintered films has a thickness of about 32 nm. Incertain examples the sintered films has a thickness of about 33 nm. Incertain other examples the sintered films has a thickness of about 34nm. In some other examples the sintered films has a thickness of about35 nm. In some examples the sintered films has a thickness of about 36nm. In some of these examples the sintered films has a thickness ofabout 37 nm. In some examples the sintered films has a thickness ofabout 38 nm. In some other examples the sintered films has a thicknessof about 39 nm. In certain examples the sintered films has a thicknessof about 40 nm. In some of these examples the sintered films has athickness of about 41 nm. In some other examples the sintered films hasa thickness of about 42 nm. In certain examples the sintered films has athickness of about 43 nm. In certain other examples the sintered filmshas a thickness of about 44 nm. In some other examples the sinteredfilms has a thickness of about 45 nm. In some examples the sinteredfilms has a thickness of about 46 nm.

In some of these examples the sintered films has a thickness of about 47nm. In some examples the sintered films has a thickness of about 48 nm.In some other examples the sintered films has a thickness of about 49nm. In certain examples the sintered films has a thickness of about 50nm. In some of these examples the sintered films has a thickness ofabout 51 nm. In some other examples the sintered films has a thicknessof about 52 nm. In certain examples the sintered films has a thicknessof about 53 nm. In certain other examples the sintered films has athickness of about 54 nm. In some other examples the sintered films hasa thickness of about 55 nm. In some examples the sintered films has athickness of about 56 nm. In some of these examples the sintered filmshas a thickness of about 57 nm. In some examples the sintered films hasa thickness of about 58 nm. In some other examples the sintered filmshas a thickness of about 59 nm. In certain examples the sintered filmshas a thickness of about 60 nm.

In some of these examples the sintered films has a thickness of about 11μm. In some other examples the sintered films has a thickness of about12 μm. In certain examples the sintered films has a thickness of about13 μm. In certain other examples the sintered films has a thickness ofabout 14 μm. In some other examples the sintered films has a thicknessof about 15 μm. In some examples the sintered films has a thickness ofabout 16 μm. In some of these examples the sintered films has athickness of about 17 μm. In some examples the sintered films has athickness of about 18 μm. In some other examples the sintered films hasa thickness of about 19 μm. In certain examples the sintered films has athickness of about 20 μm. In some of these examples the sintered filmshas a thickness of about 21 μm. In some other examples the sinteredfilms has a thickness of about 22 μm. In certain examples the sinteredfilms has a thickness of about 23 μm. In certain other examples thesintered films has a thickness of about 24 μm. In some other examplesthe sintered films has a thickness of about 25 μm. In some examples thesintered films has a thickness of about 26 μm. In some of these examplesthe sintered films has a thickness of about 27 μm. In some examples thesintered films has a thickness of about 28 μm. In some other examplesthe sintered films has a thickness of about 29 μm. In certain examplesthe sintered films has a thickness of about 30 μm. In some of theseexamples the sintered films has a thickness of about 31 μm. In someother examples the sintered films has a thickness of about 32 μm. Incertain examples the sintered films has a thickness of about 33 μm. Incertain other examples the sintered films has a thickness of about 34μm. In some other examples the sintered films has a thickness of about35 μm. In some examples the sintered films has a thickness of about 36μm. In some of these examples the sintered films has a thickness ofabout 37 μm. In some examples the sintered films has a thickness ofabout 38 μm. In some other examples the sintered films has a thicknessof about 39 μm. In certain examples the sintered films has a thicknessof about 40 μm. In some of these examples the sintered films has athickness of about 41 μm. In some other examples the sintered films hasa thickness of about 42 μm. In certain examples the sintered films has athickness of about 43 μm. In certain other examples the sintered filmshas a thickness of about 44 μm. In some other examples the sinteredfilms has a thickness of about 45 μm. In some examples the sinteredfilms has a thickness of about 46 μm. In some of these examples thesintered films has a thickness of about 47 μm. In some examples thesintered films has a thickness of about 48 μm. In some other examplesthe sintered films has a thickness of about 49 μm. In certain examplesthe sintered films has a thickness of about 50 μm. In some of theseexamples the sintered films has a thickness of about 51 μm. In someother examples the sintered films has a thickness of about 52 μm. Incertain examples the sintered films has a thickness of about 53 μm. Incertain other examples the sintered films has a thickness of about 54μm. In some other examples the sintered films has a thickness of about55 μm. In some examples the sintered films has a thickness of about 56μm. In some of these examples the sintered films has a thickness ofabout 57 μm. In some examples the sintered films has a thickness ofabout 58 μm. In some other examples the sintered films has a thicknessof about 59 μm. In certain examples the sintered films has a thicknessof about 60 μm.

In some of these examples the sintered films has a thickness of about 61μm. In some other examples the sintered films has a thickness of about62 μm. In certain examples the sintered films has a thickness of about63 μm. In certain other examples the sintered films has a thickness ofabout 64 μm. In some other examples the sintered films has a thicknessof about 65 μm. In some examples the sintered films has a thickness ofabout 66 μm. In some of these examples the sintered films has athickness of about 67 μm. In some examples the sintered films has athickness of about 68 μm. In some other examples the sintered films hasa thickness of about 69 μm. In certain examples the sintered films has athickness of about 70 μm. In some of these examples the sintered filmshas a thickness of about 71 μm. In some other examples the sinteredfilms has a thickness of about 72 μm. In certain examples the sinteredfilms has a thickness of about 73 μm. In certain other examples thesintered films has a thickness of about 74 μm. In some other examplesthe sintered films has a thickness of about 75 μm. In some examples thesintered films has a thickness of about 76 μm. In some of these examplesthe sintered films has a thickness of about 77 μm. In some examples thesintered films has a thickness of about 78 μm. In some other examplesthe sintered films has a thickness of about 79 μm. In certain examplesthe sintered films has a thickness of about 80 μm. In some of theseexamples the sintered films has a thickness of about 81 μm. In someother examples the sintered films has a thickness of about 82 μm. Incertain examples the sintered films has a thickness of about 83 μm. Incertain other examples the sintered films has a thickness of about 84μm. In some other examples the sintered films has a thickness of about85 μm. In some examples the sintered films has a thickness of about 86μm. In some of these examples the sintered films has a thickness ofabout 87 μm. In some examples the sintered films has a thickness ofabout 88 μm. In some other examples the sintered films has a thicknessof about 89 μm. In certain examples the sintered films has a thicknessof about 90 μm. In some of these examples the sintered films has athickness of about 91 μm. In some other examples the sintered films hasa thickness of about 92 μm. In certain examples the sintered films has athickness of about 93 μm. In certain other examples the sintered filmshas a thickness of about 94 μm. In some other examples the sinteredfilms has a thickness of about 95 μm. In some examples the sinteredfilms has a thickness of about 96 μm. In some of these examples thesintered films has a thickness of about 97 μm. In some examples thesintered films has a thickness of about 98 μm. In some other examplesthe sintered films has a thickness of about 99 μm. In certain examplesthe sintered films has a thickness of about 100 μm.

In certain other examples, the sintered film has a thickness of about100 nm. In other examples, the sintered film has a thickness of about500 nm. In certain other examples, the sintered film has a thickness ofabout 1 μm. In other examples, the sintered film has a thickness ofabout 2 μm. In some examples, the sintered film has a thickness of about250 nm. In some other examples, the sintered film has a thickness ofabout 2 μm. In some examples, the sintered film has a thickness of about5 μm. In some examples, the sintered film has a thickness of about 3 μm.In other examples, the sintered film has a thickness of about 4 μm. Insome examples, the sintered film has a thickness of about 300 nm. Insome examples, the sintered film has a thickness of about 400 nm. Insome examples, the sintered film has a thickness of about 200 nm.

In some of these examples the sintered films has a thickness of about101 μm. In some other examples the sintered films has a thickness ofabout 102 μm. In certain examples the sintered films has a thickness ofabout 103 μm. In certain other examples the sintered films has athickness of about 104 μm. In some other examples the sintered films hasa thickness of about 105 μm. In some examples the sintered films has athickness of about 106 μm. In some of these examples the sintered filmshas a thickness of about 107 μm. In some examples the sintered films hasa thickness of about 108 μm. In some other examples the sintered filmshas a thickness of about 109 μm. In certain examples the sintered filmshas a thickness of about 110 μm. In some of these examples the sinteredfilms has a thickness of about 111 μm. In some other examples thesintered films has a thickness of about 112 μm. In certain examples thesintered films has a thickness of about 113 μm. In certain otherexamples the sintered films has a thickness of about 114 μm. In someother examples the sintered films has a thickness of about 115 μm. Insome examples the sintered films has a thickness of about 116 μm. Insome of these examples the sintered films has a thickness of about 117μm. In some examples the sintered films has a thickness of about 118 μm.In some other examples the sintered films has a thickness of about 119μm. In certain examples the sintered films has a thickness of about 120μm. In some of these examples the sintered films has a thickness ofabout 121 μm. In some other examples the sintered films has a thicknessof about 122 μm. In certain examples the sintered films has a thicknessof about 123 jμm. In certain other examples the sintered films has athickness of about 124 μm. In some other examples the sintered films hasa thickness of about 125 μm. In some examples the sintered films has athickness of about 126 μm. In some of these examples the sintered filmshas a thickness of about 127 μm. In some examples the sintered films hasa thickness of about 128 μm. In some other examples the sintered filmshas a thickness of about 129 μm. In certain examples the sintered filmshas a thickness of about 130 μm. In some of these examples the sinteredfilms has a thickness of about 131 μm. In some other examples thesintered films has a thickness of about 132 μm. In certain examples thesintered films has a thickness of about 133 μm. In certain otherexamples the sintered films has a thickness of about 134 μm. In someother examples the sintered films has a thickness of about 135 μm. Insome examples the sintered films has a thickness of about 136 μm. Insome of these examples the sintered films has a thickness of about 137μm. In some examples the sintered films has a thickness of about 138 μm.In some other examples the sintered films has a thickness of about 139μm. In certain examples the sintered films has a thickness of about 140μm.

In some of these examples the sintered films has a thickness of about141 μm. In some other examples the sintered films has a thickness ofabout 142 μm. In certain examples the sintered films has a thickness ofabout 143 μm. In certain other examples the sintered films has athickness of about 144 μm. In some other examples the sintered films hasa thickness of about 145 μm. In some examples the sintered films has athickness of about 146 μm. In some of these examples the sintered filmshas a thickness of about 147 μm. In some examples the sintered films hasa thickness of about 148 μm. In some other examples the sintered filmshas a thickness of about 149 μm. In certain examples the sintered filmshas a thickness of about 150 μm.

iv. Nanocrystalline and Fine Grained

In some examples, provided herein is a film having grains with a d₅₀diameter less than 10 nm. In certain examples, the film has grainshaving a d₅₀ diameter less than 9 nm. In other examples, the grainshaving a d₅₀ diameter less than 8 nm. In some examples, the grains havea d₅₀ diameter less than 7 nm. In certain examples, the film has grainshaving a d₅₀ diameter less than 6 nm. In other examples, the film hasgrains having a d₅₀ diameter less than 5 nm. In some examples, the filmhas grains having a d₅₀ diameter less than 4 nm. In other examples, thefilm has grains having a d₅₀ diameter less than 3 nm. In certainexamples, the film has grains having a d₅₀ diameter less than 2 nm. Inother examples, the film has grains having a d₅₀ diameter less than 1nm.

In some examples, provided herein is a film having grains with a d₅₀diameter less than 10 μm. In certain examples, the film has grainshaving a d₅₀ diameter less than 9 μm. In other examples, the grainshaving a d₅₀ diameter less than 8 μm. In some examples, the grains havea d₅₀ diameter less than 7 μm. In certain examples, the film has grainshaving a d₅₀ diameter less than 6 μm. In other examples, the film hasgrains having a d₅₀ diameter less than 5 μm. In some examples, the filmhas grains having a d₅₀ diameter less than 4 μm. In other examples, thefilm has grains having a d₅₀ diameter less than 3 μm. In certainexamples, the film has grains having a ds diameter less than 2 μm. Inother examples, the film has grains having a d₅₀ diameter less than 1μm.

As used herein, the fine grains in the films set forth herein have d₅₀diameters of between 10 nm and 10 μm. In some examples, the fine grainsin the films set forth herein have d₅₀ diameters of between 100 nm and10 μm.

v. Free Standing

In some examples, the disclosure sets forth herein a free-standing thinfilm Garnet-type electrolyte prepared by the method set forth herein.

In some embodiments, disclosed herein is a free-standing thin filmGarnet-type electrolyte prepared by a method set forth herein.

In some embodiments, the thickness of the free-standing film is lessthan 50 μm. In certain embodiments, the thickness of the film is lessthan 40 μm. In some embodiments, the thickness of the film is less than30 μm. In some other embodiments, the thickness of the film is less than20 μm. In other embodiments, the thickness of the film is less than 10μm. In yet other embodiments, the thickness of the film is less than 5μm.

In some embodiments, the thickness of the film is less than 45 μm. Incertain embodiments, the thickness of the film is less than 35 μm. Insome embodiments, the thickness of the film is less than 25 μm. In someother embodiments, the thickness of the film is less than 15 μm. Inother embodiments, the thickness of the film is less than 5 μm. In yetother embodiments, the thickness of the film is less than 1 μm.

In some embodiments, the thickness of the film is about 1 μm to about 50μm. In certain embodiments, the thickness of the film about 10 μm toabout 50 μm. In some embodiments, the thickness of the film is about 20μm to about 50 μm. In some other embodiments, the thickness of the filmis about 30 μm to about 50 μm. In other embodiments, the thickness ofthe film is about 40 μm to about 50 μm.

In some embodiments, the thickness of the film is about 1 μm to about 40μm. In certain embodiments, the thickness of the film about 10 μm toabout 40 μm. In some embodiments, the thickness of the film is about 20μm to about 40 μm. In some other embodiments, the thickness of the filmis about 30 μm to about 40 μm. In other embodiments, the thickness ofthe film is about 20 μm to about 30 μm.

In some examples, set forth herein is a thin and free standing sinteredgarnet film, wherein the film thickness is less than 50 μm and greaterthan 10 nm, and wherein the film is substantially flat; and wherein thegarnet is optionally bonded to a current collector (CC) film comprisinga metal or metal powder on at least one side of the film.

In some examples, the thin and free standing sintered garnet film hasthickness is less than 20 μm or less than 10 μm. In some examples, thethin and free standing sintered garnet film has a surface roughness ofless than 5 μm. In some examples, the thin and free standing sinteredgarnet film has a surface roughness of less than 4 μm. In some examples,the thin and free standing sintered garnet film has a surface roughnessof less than 2 μm. In some examples, the thin and free standing sinteredgarnet film has a surface roughness of less than 1 μm. In certainexamples, the garnet has a median grain size of between 0.1 μm to 10 μm.In certain examples, the garnet has a median, grain size of between 2.0μm to 5.0 μm.

vi. Substrate Bound

In some of the films set forth herein, the film is bound to a substratethat is selected from a polymer, a glass, or a metal. In some of theseexamples, the substrate adhered to or bound to the film is a currentcollector (CC). In some of these examples, the CC film includes a metalselected from the group consisting of Nickel (Ni), Copper (Cu), steel,stainless steel, combinations thereof, and alloys thereof. In some ofthese examples, the film is bonded to a metal current collector (CC) onone side of the film. In some other examples, the film is bonded to ametal current collector (CC) on two sides of the film. In yet otherexamples, the CC is positioned between, and in contact with, two garnetfilms.

vii. Bi-Layers & Tri-Layers

In some examples, set forth herein is a trilayer including a metal foilor metal powder positioned between, and in contact with, two distinctlithium stuffed garnet thin films. In some examples, the middle layer ismetal foil. In some other examples, the middle layer is a metal powder.In some examples, the metal is Ni. In other examples, the metal is Al.In still other examples, the metal is Fe. In some examples, the metal issteel or stainless steel. In some examples, the metal is an alloy orcombination of Ni, Cu, Al, or Fe. In some examples, the trilayer has astructure as shown in FIG. 3. In some examples, the trilayer has astructure as shown in the bottom of FIG. 4. In some examples, thetrilayer has a structure as shown in the bottom of FIG. 29. In someexamples, the trilayer has a structure as shown FIG. 44(E)(F).

In some examples, set forth herein is a bilayer including a metal foilor metal powder positioned in contact with a lithium stuffed garnet thinfilm. In some examples, one layer of the bilayer is a metal foil. Inother examples, one layer of the bilayer is a metal powder. In someexamples, the metal is Ni. In other examples, the metal is Al. In stillother examples, the metal is Fe. In some examples, the metal is steel orstainless steel. In some examples, the metal is an alloy or combinationof Ni, Cu. Al, or Fe. In some examples, the bilayer has a structure asshown FIG. 44(C)(D). In some examples, the bilayer has the structureshown between the sintering plates in FIG. 20 or FIG. 21.

In some of the bilayers and trilayers described herein, the garnet ischaracterized by one of the following formula:Li_(A)La_(R)M′_(c)M″_(D)Zr_(E)O_(F),Li_(A)La_(B)M′_(C)M″_(D)Ta_(E)O_(F),Li_(A)La_(B)M′_(C)M″_(D)Nb_(E)O_(F), wherein 4<A<8.5, 1.5<B<4, 0≦C≦2,0≦D≦2; 0≦E<2, 10<F≦3, and M′ and M″ are each, independently in eachinstance selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta,or Li_(a)La_(b)Zr_(c)Al_(d)Me″_(e)O_(f), wherein 5<a<7.7; 2<b<4;0<c≦2.5; 0≦d<2; 0≦e<2, 10<f≦13 and Me″ is a metal selected from Nb, Ta,V, W, Mo, or Sb; Li_(A)La_(B)M′_(c)M″_(D)Zr_(E)O_(F), wherein the molarratio of Garnet:Al₂O₃ is between 0.05 and 0.7; or Li_(g)La₃Zr₂O₁₂.Al₂O₃,wherein 5.5<g<8.5 and the molar ratio of Garnet:Al₂O₃ is between 0.05and 1.0.

viii. Multi-Layers

In some examples, set forth herein are multiple stacks or combinationsof the aforementioned layers, bilayers, and, or, trilayers. In someexamples, two or more bilayers are stacked in serial combination. Insome other examples, two or more trilayers are stacked in serialcombination. In some examples, interposed between these serialcombination stacks are cathode active materials, anode active materials,and, or, current collectors.

ix. Film Dimensions

In some examples, the thin films set forth herein are less than 50 μm inthickness. In some other examples, the thin films set forth herein areless than 45 μm in thickness. In certain examples, the thin films setforth herein are less than 40 μm in thickness. In still other examples,the thin films set forth herein are less than 35 μm in thickness. Insome examples, the thin films set forth herein are less than 30 μm inthickness. In some other examples, the thin films set forth herein areless than 25 μm in thickness. In certain examples, the thin films setforth herein are less than 20 μm in thickness. In still other examples,the thin films set forth herein are less than 15 μm in thickness. Insome examples, the thin films set forth herein are less than 10 μm inthickness. In some other examples, the thin films set forth herein areless than 5 μm in thickness. In certain examples, the thin films setforth herein are less than 0.5 μm in thickness. In still other examples,the thin films set forth herein are less than 0.1 μm in thickness.

In some examples, provided herein is a composition formulated as a thinfilm having a film thickness of about 100 nm to about 100 μm. In certainexamples, the thickness is 50 μm. In other examples, the thickness is 40μm. In some examples, the thickness is 30 μm. In other examples, thethickness is 20 μm. In certain examples, the thickness is 10 μm. Inother examples, the thickness is 5 μm. In some examples, the thicknessis 1 μm. In yet other examples, the thickness is 0.5 μm.

In some of these examples, the films are 1 mm in length. In some otherof these examples, the films are 5 mm in length. In yet other examples,the films are 10 mm in length. In still other examples, the films are 15mm in length. In certain examples, the films are 25 mm in length. Inother examples, the films are 30 mm in length. In some examples, thefilms are 35 mm in length. In some other examples, the films are 40 mmin length. In still other examples, the films are 45 mm in length. Incertain examples, the films are 50 mm in length. In other examples, thefilms are 30 mm in length. In some examples, the films are 55 mm inlength. In some other examples, the films are 60 mm in length. In yetother examples, the films are 65 mm in length. In still other examples,the films are 70 mm in length. In certain examples, the films are 75 mmin length. In other examples, the films are 80 mm in length. In someexamples, the films are 85 mm in length. In some other examples, thefilms are 90 mm in length. In still other examples, the films are 95 mmin length. In certain examples, the films are 100 mm in length. In otherexamples, the films are 30 mm in length.

In some examples, the films are 1 cm in length. In some other examples,the films are 2 cm in length. In other examples, the films are 3 cm inlength. In yet other examples, the films are 4 cm in length. In someexamples, the films are 5 cm in length. In other examples, the films are6 cm in length. In yet other examples, the films are 7 cm in length. Insome other examples, the films are 8 cm in length. In yet otherexamples, the films are 9 cm in length. In still other examples, thefilms are 10 cm in length. In some examples, the films are 11 cm inlength. In some other examples, the films are 12 cm in length. In otherexamples, the films are 13 cm in length. In yet other examples, thefilms are 14 cm in length. In some examples, the films are 15 cm inlength. In other examples, the films are 16 cm in length. In yet otherexamples, the films are 17 cm in length. In some other examples, thefilms are 18 cm in length. In yet other examples, the films are 19 cm inlength. In still other examples, the films are 20 cm in length. In someexamples, the films are 21 cm in length. In some other examples, thefilms are 22 cm in length. In other examples, the films are 23 cm inlength. In yet other examples, the films are 24 cm in length. In someexamples, the films are 25 cm in length. In other examples, the filmsare 26 cm in length. In yet other examples, the films are 27 cm inlength. In some other examples, the films are 28 cm in length. In yetother examples, the films are 29 cm in length. In still other examples,the films are 30 cm in length. In some examples, the films are 31 cm inlength. In some other examples, the films are 32 cm in length. In otherexamples, the films are 33 cm in length. In yet other examples, thefilms are 34 cm in length. In some examples, the films are 35 cm inlength. In other examples, the films are 36 cm in length. In yet otherexamples, the films are 37 cm in length. In some other examples, thefilms are 38 cm in length. In yet other examples, the films are 39 cm inlength. In still other examples, the films are 40 cm in length. In someexamples, the films are 41 cm in length. In some other examples, thefilms are 42 cm in length. In other examples, the films are 43 cm inlength. In yet other examples, the films are 44 cm in length. In someexamples, the films are 45 cm in length. In other examples, the filmsare 46 cm in length. In yet other examples, the films are 47 cm inlength. In some other examples, the films are 48 cm in length. In yetother examples, the films are 49 cm in length. In still other examples,the films are 50 cm in length. In some examples, the films are 51 cm inlength. In some other examples, the films are 52 cm in length. In otherexamples, the films are 53 cm in length. In yet other examples, thefilms are 54 cm in length. In some examples, the films are 55 cm inlength. In other examples, the films are 56 cm in length. In yet otherexamples, the films are 57 cm in length. In some other examples, thefilms are 58 cm in length. In yet other examples, the films are 59 cm inlength. In still other examples, the films are 60 cm in length. In someexamples, the films are 61 cm in length. In some other examples, thefilms are 62 cm in length. In other examples, the films are 63 cm inlength. In yet other examples, the films are 64 cm in length. In someexamples, the films are 65 cm in length. In other examples, the filmsare 66 cm in length. In yet other examples, the films are 67 cm inlength. In some other examples, the films are 68 cm in length. In yetother examples, the films are 69 cm in length. In still other examples,the films are 70 cm in length. In some examples, the films are 71 cm inlength. In some other examples, the films are 72 cm in length. In otherexamples, the films are 73 cm in length. In yet other examples, thefilms are 74 cm in length. In some examples, the films are 75 cm inlength. In other examples, the films are 76 cm in length. In yet otherexamples, the films are 77 cm in length. In some other examples, thefilms are 78 cm in length. In yet other examples, the films are 79 cm inlength. In still other examples, the films are 80 cm in length. In someexamples, the films are 81 cm in length. In some other examples, thefilms are 82 cm in length. In other examples, the films are 83 cm inlength. In yet other examples, the films are 84 cm in length. In someexamples, the films are 85 cm in length. In other examples, the filmsare 86 cm in length. In yet other examples, the films are 87 cm inlength. In some other examples, the films are 88 cm in length. In yetother examples, the films are 89 cm in length. In still other examples,the films are 90 cm in length. In some examples, the films are 91 cm inlength. In some other examples, the films are 92 cm in length. In otherexamples, the films are 93 cm in length. In yet other examples, thefilms are 94 cm in length. In some examples, the films are 95 cm inlength. In other examples, the films are 96 cm in length. In yet otherexamples, the films are 97 cm in length. In some other examples, thefilms are 98 cm in length. In yet other examples, the films are 99 cm inlength. In still other examples, the films are 100 cm in length. In someexamples, the films are 101 cm in length. In some other examples, thefilms are 102 cm in length. In other examples, the films are 103 cm inlength. In yet other examples, the films are 104 cm in length. In someexamples, the films are 105 cm in length. In other examples, the filmsare 106 cm in length, in yet other examples, the films are 107 cm inlength. In some other examples, the films are 108 cm in length. In yetother examples, the films are 109 cm in length. In still other examples,the films are 110 cm in length. In some examples, the films are 111 cmin length. In some other examples, the films are 112 cm in length. Inother examples, the films are 113 cm in length. In yet other examples,the films are 114 cm in length. In some examples, the films are 115 cmin length. In other examples, the films are 116 cm in length. In yetother examples, the films are 117 cm in length. In some other examples,the films are 118 cm in length. In yet other examples, the films are 119cm in length. In still other examples, the films are 120 cm in length.

In some examples, the garnet-based films are prepared as a monolithuseful for a lithium secondary battery cell. In some of these cells, theform factor for the garnet-based film is a film with a top surface areaof about 10 cm². In certain cells, the form factor for the garnet-basedfilm with a top surface area of about 100 cm².

In some examples, the films set forth herein have a Young's Modulus ofabout 130-150 GPa. In some other examples, the films set forth hereinhave a Vicker's hardness of about 5-7 GPa.

In some examples, the films set forth herein have a porosity less than20%. In other examples, the films set forth herein have a porosity lessthan 10%. In yet other examples, the films set forth herein have aporosity less than 5%. In still other examples, the films set forthherein have a porosity less than 3%.

x. Composites

For Li secondary battery applications, energy density is, in part,inversely related to the amount of electrolyte, catholyte, and anolytesthat may be present. As less electrolyte, catholyte, or anolytematerials are used in a given battery architecture volume, more positiveelectrode active materials (e.g., FeF₃, CoF₂, NiF₂, CoF₂) and morenegative electrode materials (e.g., Li-metal) can be incorporated intothe same volume and thereby increase the battery's energy density, e.g.,energy per volume. It is therefore advantageous to use the methods setforth herein which, in some examples, result in film thicknesses lessthan 500 μm but greater than 1 nm, or less than 450 μm but greater than1 nm, or less than 400 μm but greater than 1 nm, or less than 350 μm butgreater than 1 nm, or less than 300 μm but greater than 1 nm, or lessthan 250 μm but greater than 1 nm, or less than 200 μm but greater than1 nm, or less than 150 μm but greater than 1 nm, or less than 100 μm butgreater than 1 nm, or less than 50 μm but greater than 1 nm, or lessthan 45 μm but greater than 1 nm, or less than 40 μm but greater than 1nm, or less than 30 μm but greater than 1 nm, or less than 35 μm butgreater than 1 nm, or less than 25 μm but greater than 1 nm, or lessthan 20 μm but greater than 1 nm, or less than 15 μm but greater than 1nm, or less than 10 μm but greater than 1 nm, or less than 9 μm butgreater than 1 nm, or less than 8 μm but greater than 1 nm, or less than7 μm but greater than 1 nm, or less than 6 μm, but greater than 1 nm, orless than 5 μm but greater than 1 nm, or less than 4 μm but greater than1 nm, or less than 3 μm but greater than 1 nm, or less than 2 μm butgreater than 1 nm, or less than 1 μm but greater than 1 nm, or less than90 nm but greater than 1 nm, or less than 85 nm but greater than 1 nm,or less than 80 nm but greater than 1 nm, or less than 75 nm μm butgreater than 1 nm, or less than 70 nm but greater than 1 nm, or lessthan 60 nm but greater than 1 nm, or less than 55 nm but greater than 1nm, or less than 50 nm but greater than 1 nm, or less than 45 nm butgreater than 1 nm, or less than 40 nm but greater than 1 nm, or lessthan 35 nm but greater than 1 nm, or less than 30 nm but greater than 1nm, or less than 25 nm μm but greater than 1 nm, or less than 20 nm butgreater than 1 nm, or less than IS nm but greater than 1 nm, or lessthan 10 nm but greater than 1 nm, or less than 5 nm but greater than 1nm, or less than 4 nm but greater than 1 nm, or less than 3 nm butgreater than 1 nm, or less than 2 nm but greater than 1 nm.

In certain examples, the garnet materials set forth herein are combinedwith polymers. In these examples, the polymers include, but are notlimited to, polyethylene oxide (PEO), polypropylene oxide (PPO). PEO-PPOblock co-polymers, styrene-butadiene, polystyrene (PS), acrylates,diacrylates, methyl methacrylates, silicones, acrylamides, t-butylacrylamide, styrenics, t-alpha methyl styrene, acrylonitriles, and vinylacetates.

In the examples herein, wherein a binder is recited (e.g., in a slurry,or in an unsintered thin film) the binder may be selected from the groupconsisting of polypropylene (PP), polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), atactic polypropylene (aPP), isotactive polypropyleneethylene propylene rubber (EPR), ethylene pentene copolymer (EPC),polyisobutylene (PIB), ZEON™, styrene butadiene rubber (SBR),polyolefins, polyethylene-co-poly-1-octene (PE-co-PO);PE-co-poly(methylene cyclopentane) (PE-co-PMCP); stereoblockpolypropylenes, polypropylene polymethylpentene copolymer and silicone.

III. LITHIUM SECONDARY BATTERIES

In some examples, the disclosure herein sets forth batteries that have acatholyte, an electrolyte, and, or, an anolyte comprised of a lithiumstuffed garnet set forth herein.

a. Battery Architectures

In some examples, the batteries described herein include a positiveelectrode (e.g., cathode) active material coated on two sides of acurrent collector substrate. In these examples, a garnet electrolyte canalso be coated onto, or within, the cathode active material.

In some examples, the disclosure herein sets forth a compositeelectrochemical device prepared by a method set forth herein; whereinthe device includes: at least one layer including a member selected fromthe group consisting of an active electrode material, a lithium stuffedgarnet electrolyte or catholyte, a conductive additive, and combinationsthereof. In some examples, the device also includes least one layerincluding a Garnet-type electrolyte.

In another embodiment, the disclosure sets forth herein a layeredmaterial for an electrochemical device, including at least one layerincluding an anode and an anode current collector, at least one layerincluding a garnet solid state electrolyte (SSE); at least one layerincluding a porous garnet in contact with the garnet SSE; wherein theporous garnet is optionally infiltrated with at least one memberselected from the group consisting of carbon, a lithium conductingpolymer, an active cathode material, and combinations thereof; and atleast one layer including an Aluminum cathode current collector incontact with the porous Garnet, wherein the porous Garnet layer is atleast 70% porous by volume; wherein the Garnet is a material selectedfrom Li_(A)La_(B)M′_(c)M″_(D)Zr_(E)O_(F),Li_(A)La_(B)M′_(c)M″_(D)Ta_(E)O_(F),Li_(A)La_(B)M′_(C)M″_(D)Nb_(E)O_(F), wherein 4<A<8.5, 1.5<B<4, 0≦C≦2,0≦D≦2; 0≦E<2, 10<F<14, and M′ and M″ are each, independently in eachinstance selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta,or Li_(a)La_(b)Zr_(c)Al_(d)Me″_(e)O_(f), wherein 5<a<7.7; 2<b<4;0<c≦2.5; 0<d≦2; 0≦e<2, 10<f<14 and Me″ is a metal selected from Nb, Ta,V, W, Mo, or Sb; and wherein the active electrode material is a cathodematerial selected from NCA (lithium nickel cobalt aluminum oxide), LMNO(lithium manganese nickel oxide), NMC (lithium nickel manganese cobaltoxide), LCO (lithium cobalt oxide, i.e., LiCoO₂), nickel fluoride(NiF_(x), wherein x is from 0 to 2.5), copper fluoride (CuF_(y), whereiny is from 0 to 2.5), or FeF_(x)(wherein z is selected from 0 to 3.5). Insome examples, 10<F<13. In some examples, 0<c≦2.

b. Battery Components Suitable for Use with Garnet Catholytes,Electrolytes, and Catholytes.

Current collectors which are suitable for use with the garnet materialsset forth herein include metal foils, metal sheets, metal wires, andmetal powders wherein the metal is a member selected from the groupconsisting of aluminum, copper, gold, nickel, cobalt, steel, stainlesssteel, lithium metal, alloys, mixtures, or combinations thereof. In someexamples, provided herein is an electrochemical device having anelectrolyte composed of a lithium stuffed garnet doped with alumina, asdescribed in this application. In some examples, provided herein is anelectrochemical device having a catholyte composed of a lithium stuffedgarnet doped with alumina, as described in this application.

In some embodiments disclosed herein, the electrode includes conductiveadditive that is carbon. In certain embodiments, the carbon is a memberselected from the group consisting of ketjen black, VGCF, acetyleneblack, graphite, graphene, nanotubes, nanofibers, the like, andcombinations thereof. In certain embodiments, the carbon is ketjenblack. In certain other embodiments, the carbon is VGCF. In yet otherembodiments, the carbon is acetylene black. In other embodiments, thecarbon is graphite. In some embodiments, the carbon is graphene. Inother embodiments, the carbon is nanotube. In other embodiments, thecarbon is nanofibers.

c. Cathode Materials Suitable for Use with the Garnet Materials SetForth Herein

The garnet materials described herein are suitable for use with avariety of cathode or positive electrode active materials. Inparticular, garnets are useful as catholytes and electrolytes becausethey are chemically compatible with conversion chemistry cathode activematerials such as, but not limited to, those active materials set forthin U.S. Nonprovisional patent application Ser. No. 13/922,214, entitledNANOSTRUCTURED MATERIALS FOR ELECTROCHEMICAL CONVERSION REACTIONS, filedJun. 19, 2013; also U.S. Nonprovisional patent application Ser. No.14/272,518, entitled PROTECTIVE COATINGS FOR CONVERSION MATERIALCATHODES, filed May 8, 2014; also U.S. Provisional Patent ApplicationNo. 62/027,908, entitled HYBRID ELECTRODES WITH BOTH INTERCALATION ANDCONVERSION MATERIALS, filed Jul. 23, 2014; and also U.S. Nonprovisionalpatent application Ser. No. 14/090,990, entitled Iron OxyfluorideElectrodes for Energy Storage, filed Nov. 26, 2013; also U.S.Nonprovisional patent application Ser. No. 14/063,966, entitled METALFLUORIDE COMPOSITIONS FOR SELF-FORMED BATTERIES, filed Oct. 25, 2013.The content of these patent applications is herein incorporated byreference in their entirety for all purposes.

The garnet materials described herein are also suitable for use withother catholyte and electrolyte materials such as, but not limited to,those catholyte and electrolyte materials set forth in International PCTPatent Application No. PCT/US 14/38283, entitled SOLID STATE CATHOLYTEOR ELECTROLYTE FOR BATTERY USING Li_(A)MP_(B)S_(C) (M=Si, Ge, and/orSn), filed May 15, 2014.

Active electrode material suitable for use with the components, devices,and methods set forth herein include, without limitation, NCA (lithiumnickel cobalt aluminum oxide), NMC (lithium nickel manganese cobaltoxide), LMNO (lithium manganese nickel oxide), LCO (lithium cobaltoxide, i.e., LiCoO₂), nickel fluoride (NiFx, wherein x is from 0 to2.5), copper fluoride (CuF_(y), wherein y is from 0 to 2.5), or FeF_(z)(wherein z is selected from 0 to 3.5). In certain embodiments, theactive electrode material is a material for a cathode. In certainembodiments, the active cathode electrode material is NCA (lithiumnickel cobalt aluminum oxide). In certain other embodiments, the activecathode electrode material is LMNO (lithium manganese nickel oxide). Inyet other embodiments, the active cathode electrode material is LCO(lithium cobalt oxide, i.e., LiCoO₂). In yet other embodiments, theactive cathode electrode material is NMC. In still certain otherembodiments, the active cathode electrode material is nickel fluoride(NiF_(x), wherein x is from 0 to 2.5). In some other embodiments, theactive cathode electrode material is copper fluoride (CuF_(y), wherein yis from 0 to 2.5). In certain other embodiments, the active cathodeelectrode material is or FeF_(z) (wherein z is selected from 0 to 3.5).

IV. METHODS OF MAKING THE MATERIALS DESCRIBED HEREIN

a. Thin Film Lithium Conducting Powder Material from Deposition Flux

In some examples, set forth herein is a process for making a batterycomponent that includes a ceramic electrolyte material (e.g., lithiumstuffed garnet powder or film) wherein one or more flux materials,having a melting point lower than 400° C. is used to mixture, dissolve,and, or, density the ceramic onto or around a substrate.

In some examples, a ceramic electrolyte powder material, or componentthereof, is mixed with two or more flux materials at a temperature ofless than 400° C. to form a fluxed powder material. This fluxed powdermaterial is shaped and heated again at a temperature less than 400° C.to form a dense lithium conducting material.

The deposition methods set forth herein are suitable for depositingmaterials, such as but not limited to, garnets, lithium stuffed garnets,perovskites, NASICON and LISICON structures.

In some examples, the deposition methods includes providing a lithiumconducting ceramic powder material at a specified quantity and density.In certain examples, the powder is characterized by, or milled to, amean particle size of about 100 nm to 10 μm. In some examples, the meanparticle size is 800 nm to 2 μm. In some of these examples, a fluxmaterial is provided at a second specified quantity and density. Incertain examples, the secondly provided flux material is less than 51%(w/w) of the first powder material. This flux material is typically alithium-containing material which melts between about 500° C. to 800° C.Additional flux materials may also be provided in the reaction mixture.In some examples, the powders and flux materials, in variouscombinations, are mixed to form eutectic mixtures. In some of theseexamples, the eutectic mixtures have a melting point less than 500° C.In some further examples, the eutectic mixtures are heated totemperature of about 100 to 500° C. In some examples, the heatedmixtures are mixed. In still other examples, the mixtures are thenheated and formed into shapes, such as but not limited to, sheets, thickfilms (greater than 100 μm thick), thin films (less than 100 μm thick)rolls, spheres, discs, sheets, pellets, and cylinders. Following areaction time and, or, additional heating, the powders and fluxmaterials are optionally cooled. In some examples, the flux is separatedor removed from the products formed therein using a solvent such as, butnot limited to, water, acetone, ethanol, or combinations thereof. Insome examples, the additional heating is to temperatures less than 500°C. This methods, and variants thereof, result in dense lithiumconducting ceramic powders, which are often 20% more dense than thestarting density of the reactants and, or, fluxes. In certain examples,the powders and flux materials include, but are not limited to, formedgarnets, such as Li₇La₃Zr₂O₁₂, and oxides, such as LiOH, La₂O₃, ZrO₂. Incertain examples, the garnet powders are formed by mixing garnetprecursors such as, but not limited to, LiOH, L₂CO₁, La₂O₃, ZrO₂, Nb₂O₅,Ta₂O₅, Al-nitrate, Al-nitrate hydrate, or combinations thereof.

In some examples, the garnet materials set forth herein are prepared bymixing garnet precursors such as, but not limited to. LiOH, La₂O₃, ZrO₂,Nb₂O₅. Ta₂O₅, Al-nitrate, or combinations thereof, to form a mixture.Next, the mixture is calcined at temperatures of 600° C. 650° C., 700°C., 750° C., 800° C., 850° C., 900° C., 950° C., 1000° C., 1050° C.,1100° C., 1150° C., 1200° C., 1250° C., 1300° C., 1350° C., 1400° C., or1.450° C. In some examples, the mixture is calcined at 800° C., 850° C.,900° C., 950° C., 1000° C. 1050° C., or 1100° C. In some examples, themixture is calcined at 800° C. In some examples, the mixture is calcinedat 850° C. In some examples, the mixture is calcined at 900° C. In someexamples, the mixture is calcined at 950° C. In some examples, themixture is calcined at 1000° C. In some examples, the mixture iscalcined at 1050° C. In some examples, the mixture is calcined at 1100°C. In some of these examples the mixture is calcined for 1, 2, 3, 4, 5,6, 7, 8, 9, or 10 hours. In some examples, the mixture is calcined for4, 5, 6, 7, or 8 hours. In some examples, the mixture is calcined for 4hours. In some examples, the mixture is calcined for 5 hours. In someexamples, the mixture is calcined for 6 hours. In some examples, themixture is calcined for 7 hours. In these examples, the calcinationtemperature is achieved by a heating ramp rate of about 1 C/min or about5 C/min or about 10 C/imin. In some of these examples, the calcinedmixture is then milled to break-up any mixture agglomerates. In some ofthese examples, the calcined mixture is then milled to reduce the meanprimary particle size. In certain examples, the milled calcined mixtureis then sintered at temperatures of 600° C., 650° C., 700° C., 750° C.,800° C., 850° C., 900° C., 950° C., 1000° C., 1050° C., 1100° C., 1150°C., 1200° C., 1250° C., 1300° C., 1350° C., 1400° C., or 1450° C. Insome examples, the sintering is at temperatures of 1000° C., 1050° C.,1100° C., 1150° C., 1200° C., 1250° C., 1300° C., 1350° C., 1400° C., or1450° C. In some examples, the sintering is at temperatures of 1000° C.,1200° C. or 1400° C. In these examples, the sintering is for 1, 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23,24, 25, 26, 27, 28, 29, or 30 minutes.

In some examples, the flux includes inorganic salts, such as lithium,sodium, potassium, and rubidium salts. For example, LiF, LiCl, LiBr,and, or, LiI. In some examples, the flux includes inorganic oxides, suchas LiOH, Li₂CO. Flux may also include alkali metal hydroxides,chlorides, nitrates, sulphates, and combinations thereof. Certaincombinations that are useful include mixtures of any one or more membersselected from the group consisting of LiOH, LiCl, LiBr, LiI, LiNO₃,LiSO₄, Li₂O—SiO₂, Li₂O—B₂O, Li₂O—PbO, Li₂O—Bi₂O₃, NaOH, NaCl, NaNO₃,NaSO₄, NaBr, Na₂CO₃, KOH, KCl, KNO₃, KSO₄, KBr, and K₂COC₃.

Flux include eutectic mixtures of materials, wherein the eutecticmixture has a lower melting point than the melting point any of theconstituent components of the mixture. For example, a mixture having0.3LiOH and 0.7NaOH melts around 250° C., which is lower than themelting point for either LiOH or NaOH.

In some examples, the powders, fluxes, and reaction mixtures aredeposited onto current collectors, positive electrodes, negativeelectrodes, or electrolytes.

In some examples, powders synthesized herein are mixed with fluxcomponents in order to dissolve the powders in the flux components.These fluxes having dissolved powders are cast onto a substrate to forma film having a thickness between about 10 nm and about 250 μm. In someexamples, the casting onto a substrate is accomplished through slotcasting, doctor blade casting, or by dip coating a substrate into theflux.

In some other examples, powders synthesized herein are mixed with fluxcomponents and also a liquid or solvent in order to prepare a slurry ofthese components. The slurry is then cast onto a substrate to form afilm having a thickness between about 10 nm and about 250 μm. In someexamples, the casting onto a substrate is accomplished through slotcasting, doctor blade casting, or by dip coating a substrate into theflux. The slurry is then dried to remove the solvent and, optionally,melt and mix the flux components and the powders. In some examples, theheating is accomplished at 1° C./min and to a temperature of about 200°C., or about 250° C., or about 300° C., or about 350° C., or about 350°C., or about 400° C., or about 450° C., or about 500° C. In someexamples, more flux than synthesized powders are used so as tocompletely dissolve the powders in the flux. In other examples, moresynthesized powders than flux is used to as not to dissolve all of thepowders in the flux.

In some examples, positive electrode active materials are mixed withgarnet powders and also flux components to form a mixture. This mixturecan be deposited onto one, two, or more sides of a current collector.Once the flux is processed, as set forth herein, and optionally removed,an intimate mixture of garnet materials and active materials remain indirect contact with a current collector.

In any of these examples, the substrate, e.g., current collector, can becoated with a garnet material optionally including a positive electrodeactive material by dip coating the substrate into a flux having thegarnet, garnet precursors, active material, or combinations thereof. Inany of these examples, the substrate, e.g., current collector, can becoated with a garnet material optionally including a positive electrodeactive material by casting the flux having the garnet, garnetprecursors, active material, or combinations thereof onto the substrate.In these examples, casting can be doctor blade casting. In theseexamples, casting can be slot casting. In these examples, casting can bedip coating.

In some examples, the methods herein include providing a lithiumconducting ceramic powder material in a eutectic mixture of one or moreflux materials; heating the mixture to a temperature of about 400° C. toabout 800° C.; optionally casting the flux material; and forming a denselithium conducting garnet material. In some examples, the formedmaterial is 20% or more dense than the precursors thereto. In someexamples two flux materials are used, in which the first flux is one ormore materials selected from LiOH, LiCl, LiBr, LiNO₃, LiSO₄, orcombinations thereof, and in which the second flux is one or morematerials selected from NaOH, NaCl, NaNO₃, NaSO₃, NaSO₄, NaBr, Na₂CO₃,or combinations thereof. In some examples, the powder material is alithium stuffed garnet. In some examples, the powder material optionallyincludes a perovskite material. In some examples, the powder materialincludes NASICON, LISICON, or a Tungsten/Bronze material. In someexamples a third flux is provided in this method and is one or morematerials selected from KOH, KCl, KNO₃, KSO₄, KBr, and, or, K₂CO₃.

Additional details, examples, and embodiments of these methods of makinggarnet materials is found, for example, in U.S. Provisional PatentApplication No. 61/887,451, filed Oct. 7, 2013, entitled METHOD ANDSYSTEM FOR FORMING GARNET MATERIALS WITH SINTERING PROCESS, the contentsof which are herein incorporated by reference in their entirety for allpurposes.

As shown in FIG. 1, in some examples precursors are, optionally milledand, mixed with a flux (step a) and heated to dissolve the precursors inthe flux (step b). The flux with dissolved precursors is cast (step c)and calcined (step d) to react the precursors and for larger and morecrystalline particles (step e) which are densified by the flux. In someexamples, the flux is removed (step f).

b. Solutions and Slurries

In some examples, the methods herein include the use of solutions andslurries which are cast or deposited onto substrates. In certainexamples, garnet precursors are milled according to the milling methodsset forth herein. In some examples, these precursors are formulated intoa slurry. In some examples, these milled precursors are formulated intoa slurry. After milling, in some examples, the precursors are formulatedinto coating formulations, e.g., slurries with binders and solvents.These slurries and formulations solvents, binders, dispersants, andsurfactants. In some examples, the binder polyvinyl butyral (PVB) andthe solvent is toluene and/or ethanol and/or diacetone alcohol. In someexamples, PVB is both a binder and a dispersant. In some examples, thebinders also include PVB, PVP, Ethyl Cellulose, Celluloses, PVA, andPVDF. In some examples, the dispersants include surfactants, fish oil,fluorosurfactants, Triton. PVB, and PVP. In some slurries, 10% to 60% byweight (w/w) of the slurry is solid precursors. Binders and dispersantscan each, in some slurries, make up 50% w/w of the slurry, with solventscomprising the remainder weight percentages.

In some examples disclosed herein, slurries include a conductiveadditive that is carbon. In certain embodiments, the carbon is a memberselected from the group consisting of ketjen black, VGCF, acetyleneblack, graphite, graphene, nanotubes, nanofibers, the like, andcombinations thereof. In certain embodiments, the carbon is ketjenblack. In certain other embodiments, the carbon is VGCF. In yet otherembodiments, the carbon is acetylene black. In other embodiments, thecarbon is graphite. In some embodiments, the carbon is graphene. Inother embodiments, the carbon is nanotube. In other embodiments, thecarbon is nanofibers.

In some examples, the solvent is selected from toluene, ethanol,toluene:ethanol, or combinations thereof. In certain embodimentsdisclosed herein, the binder is polyvinyl butyral (PVB). In certainembodiments disclosed herein, the binder is polypropylene carbonate. Incertain embodiments disclosed herein, the binder is apolymethylmethacrylate.

In some examples, the solvent is toluene, ethanol, toluene:ethanol, orcombinations thereof. In some examples, the binder is polyvinyl butyral(PVB). In other examples, the binder is polypropylene carbonate. In yetother examples, the binder is a polymethylmethacrylate.

In some embodiments disclosed herein, the removing the solvent includesevaporating the solvent. In some of these embodiments, the removing thesolvent includes heating the film. In some embodiments, the removingincludes using a reduced atmosphere. In still other embodiments, theremoving includes using a vacuum to drive off the solvent. In yet otherembodiments, the removing includes heating the film and using a vacuumto drive off the solvent.

c. Catholytes

As shown in FIG. 25, one method of making an embodiment of an inventiondisclosed herein includes depositing a dense, solid state separatorelectrolyte for the anode and optionally sintering the electrolyte. Insome embodiments, the method also includes depositing a porous garnetcatholyte and sintering the catholyte to achieve greater than 70%porosity. In some embodiments, the method also includes filling theporous catholyte with less than 10 volume % carbon by a method selectedfrom chemical vapor deposition (CVD), pyrolysis, or a related technique.In some embodiments, the method also includes filling the porouscatholyte with an ion conductive flowable material such as liquid, gel,or polymer. In some embodiments, the method also includes filling withthe active material. In certain embodiments, the methods achieves anactive material loading greater than 40 volume %. In some embodiments,the methods also include laminating or evaporating the cathode currentcollector.

In some embodiments, disclosed herein is a method for making a compositeelectrochemical device, including the following step, in any order:providing an anode layer comprising an anode current collector;providing a Garnet-type solid state electrolyte (SSE) layer in contactwith at least one side of the anode layer and optionally sintering theSSE; providing a porous Garnet layer in contact with the SSE layer andoptionally sintering the porous Garnet layer; optionally infiltratingthe porous Garnet layer with at least one member selected from the groupconsisting of carbon, a lithium conducting polymer, an active cathodematerial, and combinations thereof; and providing a cathode currentcollector layer in contact with the porous Garnet layer. In someexamples, these steps are performed sequentially in the order in whichthey are recited.

In some examples, the methods set forth herein further include providinga layer of a Garnet-type solid state electrolyte (SSE) on twoindependent sides of the anode current collector layer.

In some examples, the sintering includes heat sintering or fieldassisted sintering (FAST); wherein heat sintering comprises heating theGarnet in the range from about 800° C. to about 1200° C. for about 1 toabout 600 minutes; and wherein FAST sintering comprises heating theGarnet in the range from about 600° C. to about 800° C. and applying aD.C. or A.C. electric field to the Garnet.

In some examples, the infiltrating the porous Garnet layer with carbonincludes using chemical vapor deposition (CVD) or pyrolysis.

In some examples, the infiltrating the porous Garnet layer with anactive material includes using vapor/liquid deposition orelectrophoretic deposition.

In some examples, the providing a cathode current collector in contactwith the porous Garnet layer includes laminating, electroplating orevaporating the current collector onto the porous Garnet layer.

In some examples, the porous Garnet layer is at least 70% porous byvolume after it is sintered.

In some examples, the porous Garnet layer is characterized by a Liconductivity of 1e-3S/cm or greater at 60° C. In some examples, thelithium conductive polymer is characterized by a Li conductivity of1e-4S/cm or greater at 60° C. In those examples wherein a material setforth herein is characterized by a Li conductivity of 1e-4S/cm orgreater at 60° C., the conductivity is a measurement of the bulkconductivity. In some of these examples, the conductivity is measured sothat the conduction occurs through the material but unaffected by theporosity of the material.

In some examples, the porous Garnet layer has pores with average porediameter dimensions of about 5 nm to about 1 μm.

In some examples, the polymer is stable at voltages greater than about3.8V.

In some examples, the porous Garnet layer is characterized by aconductivity of about σ_(i)>1e-3 S/cm at 60° C.

In some examples, the porous Garnet layer is infiltrated with the activecathode material in an amount greater than 40% by volume. In someexamples, the porous Garnet layer is infiltrated with the active cathodematerial in an amount greater than 55% by volume.

In some examples, the Garnet is stable at voltages of about 1.3V toabout 4.5V.

In some examples, the Garnet is a material selected fromLi_(A)La_(B)M′_(c)M″_(D)Zr_(E)O_(F),Li_(A)La_(B)M′_(c)M″_(D)Ta_(E)O_(F),Li_(A)La_(B)M′_(C)M″_(D)Nb_(E)O_(F), wherein 4<A<8.5, 1.5<B<4, 0≦C≦2,0≦D≦2; 0≦E<2, 10<F<13, and M′ and M″ are each, independently in eachinstance selected from Al, Mo, W, Nb, Sb, Ca. Ba, St, Ce, Hf, Rb, or Ta,or Li_(a)La_(b)Zr_(e)Al_(d)Me″_(e)O_(f), wherein 5<a<7.7; 2<b<4;0<c≦2.5; 0≦d<2; 0≦e<2, 10<f<13 and Me″ is a metal selected from Nb, Ta,V, W, Mo, or Sb.

In some examples, the active electrode material is a cathode materialselected from NCA (lithium nickel cobalt aluminum oxide), LMNO (lithiummanganese nickel oxide), LCO (lithium cobalt oxide, i.e., LiCoO₂), NMC,nickel fluoride (NiF_(x), wherein x is from 0 to 2.5), copper fluoride(CuF_(y), wherein y is from 0 to 2.5), or FeF_(z) (wherein z is selectedfrom 0 to 3.5). In some examples, disclosed herein is an electrochemicaldevice prepared by a methods set forth herein.

As shown in FIG. 27 and FIG. 29, the methods set forth herein processesfor preparing a composite electrode for a solid state battery composedof active electrode materials with interspersed electrolyte particlesprior to any sintering treatment. In some embodiments, the layer canalso contain an electrically conductive additive (e.g. carbon).

As shown in FIG. 31, the electrolyte and electrode materials haveimproved interfacial contact after sintering occurs. In someembodiments, a free-standing, bilayer, or trilayer garnet film, setforth herein, is bonded to Lithium. The Li-garnet interface in theseexamples has an unexpectedly low area specific resistance (ASR). In someexamples, the ASR is less than 5 Ohm cm² at 80° C. In some examples, theASR is less than 100 Ohm cm² at 80° C. In some examples, the ASR isabout 1 Ohm cm² at 80° C. In some examples, the ASR is less than 6 Ohmcm² at 80° C.

In some embodiments, Li is evaporated or laminated to a sintered garnetfilm (free standing, bilayer, or trilayer) and has a low ASR. In someexamples, the ASR is less than 5 Ohm cm² at 80° C. In some examples, theASR is less than 100 Ohm cm² at 80° C. In some examples, the ASR isabout 1 Ohm cm² at 80° C. In some examples, the ASR is less than 6 Ohmcm² at 80° C.

As shown in FIG. 15, FIG. 16, FIG. 17, FIG. 20, FIG. 21, and FIG. 28setter plates can be used to sinter particles with the use of a powersupply that can apply in some examples, an A.C. current, and in someother examples, a D.C. current.

As shown in FIG. 4, electrochemical devices can be prepared by thesintering methods set forth herein. In FIG. 4, for example, anelectrolyte powder, catholyte particles (e.g., Garnet catholyte), andactive electrode particles (e.g., cathode active particles) can belayered and mixed and then sintered according to the novel methods setforth herein.

In some examples, the films set forth herein can be initially formed inthe “green” (unsintered) state by preparing a slurry of the powderedceramic component(s) (e.g. electrolyte: Lithium stuffed garnet, LithiumLanthanum, Zirconium Oxide; electrode: Lithium-Nickel-Manganese-Cobaltoxide) with an organic binder-solvent system (e.g. polyvinyl butyral intoluene:ethanol). In some examples of the composite electrode, inaddition to the electrolyte and active electrode material, a conductiveadditive such as carbon black can also be added to increase electricalconductivity in the final product. The slurry can be cast as a thinlayer typically of thickness 10-100 μm. The solvent is evaporated toleave behind a flexible membrane which is easily handled and can belaminated to other such layers by applying a small pressure (<0.1000psi) at modest temperature (80° C.). For example, a green composite thinfilm of a Li-conducting garnet electrolyte and a high voltage cathodematerial (NMC) is shown, for examples in FIG. 27.

Some of the example methods set forth herein include heat sintering.

In some examples, after a binder burnout step to remove the binder(e.g., PVB) a composite electrode such as that shown in FIG. 27 can beheated to an elevated temperature (e.g. 800-1200° C.) and held for aperiod of time (1-600 mins) to induce sintering of the particles to forma much denser matrix. In some of these examples, the grains of theindividual components will fuse together to significantly increase theircontact area, for example as shown in FIG. 27. In some examples, it isadvantageous to use finely milled powder, especially for the electrolytecomponent, as this increases sintering kinetics and permitsdensification at lower temperatures. To maintain the flatness of a thinmembrane under this process the films can be sandwiched between inertsetter plates such as porous zirconia. This not only keeps the filmslaminar, but provides a pathway for release of the binder decompositionproducts. The resulting microstructure of the sintered electrodecomposite is shown in FIG. 30, FIG. 31, for example.

Some of the example methods set forth herein include field assistedsintering (i.e., FAST) sintering

One drawback of the conventional sintering process is that it requiresextended dwell times at elevated temperatures where several detrimentalphenomena can occur. For example, Lithium is a highly volatile speciesand can evaporate from the solid state electrolyte material therebyreducing its ionic conductivity, inducing surface depleted layers ofhigh resistance or even causing decomposition of the material. In thecase of the composite layers, the electrolyte and electrode componentswill continue to interact once the grains have fused together and theymay inter-diffuse to such an extent that the electrochemical propertiesof the individual components are lost i.e. the electrolyte may lose itsionic conductivity, or the electrode may lose it propensity to store theactive ion (e.g. Lithium). Therefore, to overcome all these problems, itis advantageous to make the sintering process as fast as possible. Insome examples, this is achieved using field assisted sintering.

FIG. 16, FIG. 17, FIG. 18, FIG. 19, FIG. 20, FIG. 21, FIG. 22 showschematic representations of the arrangement to FAST sinter anelectrolyte membrane at lower temperatures (e.g., 600-800° C., or less)or (400-1000° C.) than the conventional sintering process (˜1100° C.) isdisclosed herein. The membrane is sandwiched between two conductivemetal plates, while held in an oven at a modest temperature (800 C)where Lithium evaporation is not significant. An electric field is thenapplied to the sample to induce FAST sintering. The field can be a D.C.field or an A.C. field. In some examples, the A.C. field is advantageousas a sufficiently high frequency can be selected so that the ionicspecies do not segregate significantly under the stimulus. Powerdelivery to the sample must be controlled to avoid excessive jouleheating of the material. In some examples, this can be accomplished byinitially operating in a constant voltage amplitude mode and switchingto constant current once the sintering begins and the impedance of thesample falls. The electrolyte membrane can be sintered to full densityin a much shorter time and at a lower temperature than the conventionalprocess.

In some examples, FAST sintering also overcomes the problem ofinterdiffusion in the composite electrode layers.

FIG. 29 shows a schematic illustration of the arrangement of a fullsolid state battery configuration under FAST sintering. The electrolytelayer is laminated to the composite electrode layer prior to sintering.The benefit of the FAST sintering process is that the voltage drop(i.e., the electric field) is distributed preferentially over the highimpedance regions, which will always be the areas of poor contact (i.e.,non-sintered regions). Therefore, once two particles sinter together,the contact between the constituent particles improves and theresistance drops. Consequently, the E-field distribution shifts to aneighboring unsintered particles. In this way the driving force forsintering is shifted away from grains that are already fused togetherand further interdiffusion is limited.

These sintering methods are advantageous for solid state batteries andcomponents thereof, which do not include liquid electrolytes, on accountof fast sintering times, limited interdiffusion between the componentsin a composite electrode, and also the ability to prepare a full solidstate battery arrangement.

d. Doped Compositions

In some examples, provided herein are methods for making a lithiumstuffed garnet doped with aluminum, the methods comprising providinggarnet precursors at predetermined combination. In some examples, themethods further include milling the combination for 5 to 10 hours. Inother examples, the methods further comprising calcining the combinationin vessels at about 500° C. to about 1200° C. for about 4 to about 10hours to form a garnet. In other examples, the methods further includemilling the formed garnet until the d₅₀ particle size is between 200 and400 nm. In still other examples, the methods further include mixing themilled forming garnet with a binder to form a slurry. In some of theseexamples, before the slurry is sintered, the methods include providing agreen film by casting the slurry as a film. In other examples, themethods further include filtering the slurry. In still other examples,the methods further include optionally providing pellets of filteredslurry. In some of these examples, before the slurry is sintered, themethods include providing a green film by casting the slurry. In stillother examples, the methods further include sintering the filteredslurry. In the examples wherein the slurry is sintered, sinteringincludes applying pressure to the slurry with setting plates, heatingthe slurry under flowing inert gas between 140° C. and 400° C. for about1 to about 6 hours, and either heat sintering or field assistedsintering for about 10 minutes to about 10 hours.

In certain examples, the garnet precursor are selected fromLiOH_(x)La₂O₃, ZrO₂ and Al(NO₃)₃.9H₂O.

In some examples, the garnet precursors are calcined in vessels is at900° C. for 6 hours. In certain examples, the vessels are Alumina (i.e.,Al₂O₃) vessels.

In certain examples, the milling the formed garnet is conducted untilthe d₅₀ particle size of the formed garnet is about 300 nm. In certainother examples, the milling the formed garnet is conducted until the d wparticle size of the formed garnet is about 100 nm. In some examples,the milling the formed garnet is conducted until the d₅₀ particle sizeof the formed garnet is about 200 nm. In certain examples, the millingthe formed garnet is conducted until the d₅₀ particle size of the formedgarnet is about 250 nm. In certain examples, the milling the formedgarnet is conducted until the d₅₀ particle size of the formed garnet isabout 350 nm. In certain examples, the milling the formed garnet isconducted until the d₅₀ particle size of the formed garnet is about 400nm.

In some examples, the mixing the milled forming garnet with a binder toform a slurry includes about 4% w/w binder. In some examples, the binderis polyvinyl butyral.

In some examples, the filtering the slurry includes filtering with an 80mesh sieve.

In some examples, the providing pellets of filtered slurry includesproviding pellets having a 13 mm diameter. In some examples, the pelletshave a 10 mm, 11 mm, 12 mm, 13 mm, 14 mm, 15 mm, 16 mm, 17 mm, 18 mm, 19mm, or 20 mm diameter.

In some examples, the applying pressure to the slurry with settingplates includes applying a pressure of 3 metric tons. In some otherexamples, the applying pressure to the slurry with setting platesincludes applying a pressure of 2 metric tons. In some examples, theapplying pressure to the slurry with setting plates includes applying apressure of 1 metric tons. In some examples, the applying pressure tothe slurry with setting plates includes applying a pressure of 3.5metric tons.

In some examples, the setter plates are Pt setter plates. In otherexamples, the setter plates are garnet setter plates. In certainexamples, the setter plates are porous setter plates. In yet otherexamples, the setter plates are porous garnet setter plates. In yetother examples, the setter plates are porous zirconia setter plates.

In some examples, the methods include flowing inert gas as an Argon gasflowing at a flow rate or 315 sccm.

In some examples, the methods set forth herein include heating theslurry under flowing inert gas including separate dwells at 160° C. and330° C. for 2 hours (hrs) each under a humidified Argon flow.

e. Fine Grain Lithium Stuffed Garnets

In some examples, provided herein are methods of making thin films withfine grains of lithium stuffed garnets doped with alumina. In someexamples, in order to make these fine grains, the films described hereinare heat sintered at a maximum temperature of 1150° C. In some examples,in order to make these fine grains, the films described herein are heatsintered at a maximum temperature of 1150° C. for no more than 6 hours.In some examples, in order to make these fine grains, the filmsdescribed herein are heat sintered at a maximum temperature of 1075° C.In some examples, in order to make these fine grains, the filmsdescribed herein are heat sintered at a maximum temperature of 1075° C.for no more than 6 hours. In certain examples, when the films are onlysintered for 15 minutes, heat sintering temperatures of 1200° C., at amaximum, are used.

Grains grow larger as temperature is increased. Also, grains grow largerat a given temperature while the dwell time at that temperature isincreased. For this reason, the methods set forth herein include heatsintering at temperatures less than 1200° C., or less than 1150° C., orless than 1075° C. In some of these examples, the methods set forthherein include heat sintering at these temperatures for no more than 6hours. In some examples, the methods set forth herein include heatingsintering for no more than 15 minutes. In some other examples, themethods set forth herein include heat sintering at 1050° C. In someother examples, the methods set forth herein include heat sintering at1000° C. In some other examples, the methods set forth herein includeheat sintering at 950° C. In some other examples, the methods set forthherein include heat sintering at 900° C. In some other examples, themethods set forth herein include heat sintering at 850° C. In some otherexamples, the methods set forth herein include heat sintering at 800° C.In some other examples, the methods set forth herein include heatsintering at 750° C. In some other examples, the methods set forthherein include heat sintering at 700° C. In some other examples, themethods set forth herein include heat sintering at 650° C. In some otherexamples, the methods set forth herein include heat sintering at 600° C.In some other examples, the methods set forth herein include heatsintering at 550° C. In some other examples, the methods set forthherein include heat sintering at 500° C. In some other examples, themethods set forth herein include heat sintering at 450° C. In some otherexamples, the methods set forth herein include heat sintering at 400° C.In some other examples, the methods set forth herein include heatsintering at 350° C. In some other examples, the methods set forthherein include heat sintering at 300° C. In some other examples, themethods set forth herein include heat sintering at 250° C. In some otherexamples, the methods set forth herein include heat sintering at 200° C.In some other examples, the methods set forth herein include heatsintering at 150° C.

In some examples, smaller amounts of Li in the lithium stuffed garnetlead to smaller grains in the films set forth herein

f. Casting

In some examples, the slurries set forth herein are deposited ontosubstrates using casting techniques including slot dye coating, slotcasting, doctor blade casting, mold casting, roll coating, gravure,microgravure, screen printing, flexoprinting, and/or other relatedmethods.

Other casting methods are set forth in U.S. Provisional PatentApplication No. 61/887,451, filed Oct. 7, 2013, entitled METHOD ANDSYSTEM FOR FORMING GARNET MATERIALS WITH SINTERING PROCESS, and U.S.Provisional Patent Application No. 61/926,910, filed Jan. 13, 2014,entitled GARNET THIN FILM ELECTROLYTE, and U.S. Provisional PatentApplication No. 62/007,417, filed Jun. 4, 2014, entitled METHODS ANDSYSTEMS FOR FORMING GARNET MATERIAL WITH REACTIVE SINTERING, and U.S.Provisional Patent Application No. 62/026,271, filed Jul. 18, 2014,entitled FINE GRAINED LITHIUM-ION CONDUCTING THIN FILM GARNET CERAMICS,and U.S. Provisional Patent Application No. 62/026,440, filed Jul. 18,2014, entitled GARNET CATHOLYTE AND SINTERING OF SOLID STATEELECTROCHEMICAL DEVICES AND COMPONENTS. Each of these provisional patentapplications is incorporated by reference herein for all purposes intheir entirety.

g. Sintering Methods

While certain solid state ionic conductors can be sintered in aconventional process by pressing small pellets, which are approximately10 mm in diameter and 2 mm thick in thickness, known methods for makingthin films of garnet based materials are insufficient for batteryapplications, which require film lateral dimensions of approximately 10cm and between 100 nm to 50 μm in thickness.

Sintering thin films, particularly films that include garnet (e.g.,lithium-stuffed garnet), using applied electrical currents and voltagesis inherently challenging. In part, this is related to the resistiveheating that occurs in the garnet material when current flowsthere-through and thereby causes a sintering effect. For example, whenelectricity is used to sinter garnet, as is done with FAST sintering,the electricity resistively heats and sinters the garnet materialprimarily where the impedance is the greatest. As the garnet is sinteredand the impedance decreases, the resistive heat associated with anelectrical current passing through the garnet also decreases. As theimpedance decreases in certain portions of the garnet material, thepassed electrical current primarily takes the path of least resistance(i.e., the path where the impedance is lowest) and does not resistivelyheat the unsintered portions of the garnet where the impedance issignificantly higher. As more garnet sinters, and the impedancedecreases, it becomes more difficult to sinter the remaining unsinteredportions of the garnet and particularly so where the impedance isgreatest due to the garnet portions where the impedance is smallest.

In order to overcome this challenge, some persons use a cylindrical formfactor such as that shown in FIG. 15. By directing an applied electricalcurrent between electrodes spaced at the extreme longitudinal ends of acylinder, these persons overcome the aforementioned challenges since theelectrical current passes through the longest portion of the sinteringmaterial. However, for several of the applications considered herein andwith the instant patent application, a form factors that is a thin filmis required. In some examples, this form factor is rectangular withrespect to its shape. In some other examples, this form factor isrectangular-like with respect to its shape. These films, thin films, andrectangular-like form factors are difficult to sinter in part becausethe electrodes, through which an electrical current is applied, do nottransmit electricity through the longest portion of the film sample. Forthin films, the applied electrical current passes through thez-direction of the film, which is one of the shorter paths through thebulk of the material.

In addition to the aforementioned challenges, for many applications itis preferable that the thin film densify primarily in the z-directionand not in the x- or y-directions (as shown in FIG. 23). This means thatthe shrinkage of the film is primarily in the z-direction and more sothan in either the x- or the y-direction. Accomplishing this type ofdensification and shrinkage is also a challenge met by the instantapplication. The present application sets forth several sinteringmethods for overcoming these and other sintering challenges.

As shown in FIG. 24 of FIG. 45, an example sintering methods includesplacing electrodes on a thin film form factor so that an appliedelectrical current passes through the z-direction of the film. In thisorientation, FAST sintering is employed according to a sintering methodsset forth herein.

As shown in FIG. 16, another example sintering method includes usingsintering plates. In some examples, the applied electrical currentpasses through the sintering plates. In some other examples, the appliedelectrical current passes through the sintering plates while a pressureis applied according to the pressure values recited in this applicationherein and above. In certain other examples, the applied electricalcurrent is applied directly to the thin film while the setter platesindependently apply a pressure according to a pressure value recited inthis application, herein and above. In yet certain other examples, oneor more metal foil layers are inserted between a setter plate and thethin film and the applied electrical current is applied to the insertedmetal foil.

FIG. 20 shows an example where a metal foil is places between a sinteredfilm and setter plates. In some examples, a metal powder is insertedbetween the setter plates and the garnet film to be sintered. In some ofthese examples, as the garnet film is sintered, the metal powder alsosinters and adheres to the sintering film.

FIG. 21 shows an example where a metal powder is places between asintered film and setter plates.

In some of these examples, the setter plate is a porous setter plate. Insome of these examples, the setter plate is a garnet-based setter plate.In some of these examples, the setter plate is a porous garnet-basedsetter plate. In some of these examples, the setter plate is a metallicsetter plate. As used herein, garnet-based setter plates includes asetter plate that comprises a garnet material described herein.

As shown in FIG. 17, in some examples the plates used for sintering andoptionally for applying pressure can have individually addressablecontact points so that the applied electrical current is directed tospecific positions on the sintering film. As shown in FIG. 17, thetapered ended of the plurality of trapezoid-like shapes (100) indicatesthese individually addressable contacts points. As used herein,individually addressable refers to the ability to controllable andindividually apply a current or a voltage to one contact point that maybe different from the controllably applied current or voltage applied toanother contact point.

In some examples the plates used for sintering and optionally forapplying pressure can have grid structure. In some examples, this gridstructure is movable so that it can be placed on the sintering film atdifferent positions during the sintering process.

As shown in FIG. 18, in some examples the thin film form factor issintered while it moves through calender rollers. In these examples, thecalender rollers apply a pressure according to a pressure value setforth herein and also provide a conduit for an applied electricalcurrent or voltage as necessary for sintering, e.g., FAST sintering. InFIG. 18, the larger arrow, which is not surrounded by a circle and isparallel to the x-direction of the film, indicates the direction ofmovement of the sintering film as it moves through the calender rollers.

As shown in FIG. 19, in some of the examples where a thin film formfactor is sintered while it moves through calender rollers, the calenderrollers have individually addressable contact points (200) so that anelectrical current or voltage can be applied controllably andindividually to the sintering film at different positions.

As shown in FIG. 19, in some of the examples where a thin film formfactor is sintered while it moves through calender rollers, one of thecalender rollers is a ground electrode.

As shown in FIG. 22, in some of the examples wherein a thin film formfactor is sintered while it moves through calender rollers, one of thecalender rollers is a spiral design that can rotate about itslongitudinal axis and also move parallel to its longitudinal axis. Thisspiral design allows for the applied electrical current or voltage to bedirected to the sintering film.

i. Reactive Sintering

In some examples, the set forth herein are reactive sintering methods.In these examples, garnet precursors are mixed to form a mixture. Inthese examples, the precursors include the garnet precursors set forthin the instant patent application. In some examples, the mixture ismilled according to the milling methods set forth in the instant patentapplication. In some examples, the mixture is formulated as a slurry ofmilled precursor materials to form a slurry. In some examples, theslurry is then coated onto a substrate by methods such as, but notlimited to, doctor blade casting, slot casting, or dip coating. In someother examples, the slurry is cast onto a substrate according to acasting method set forth in the instant patent application. In some ofthese examples, the slurry is then dried to remove the solvent or liquidtherein. In some examples, the dried slurry is calendered. In someadditional examples, the dried slurry is laminated to other layers ofbattery components. In some of these examples, pressure is applied toadhere or bond the laminated layers together. In certain examples, thedried slurry layers to which pressure is applied are sintered accordingto the methods set forth herein. In those examples, wherein sinteringoccurs with garnet precursors in a slurry or dried slurry format, thesintering occurs simultaneous with a chemical reaction of the garnetprecursors to form sintered garnet.

In some examples, reactive sintering includes mixing garnet precursorswith preformed garnet powder and sintering the mixture using temperatureand, or, an applied current. In some examples, the ratio of garnetprecursors to garnet powder is 10:90. In some examples, the ratio ofgarnet precursors to garnet powder is 20:80. In some examples, the ratioof garnet precursors to garnet powder is 25:75. In some examples, theratio of garnet precursors to garnet powder is 50:50. In some examples,the ratio of garnet precursors to garnet powder is 60:40. In someexamples, the ratio of garnet precursors to garnet powder is 70:30. Insome examples, the ratio of garnet precursors to garnet powder is 75:25.In some examples, the ratio of garnet precursors to garnet powder is80:20. In some examples, the ratio of garnet precursors to garnet powderis 90:10.

ii. Tapecasting

In some examples, set forth herein are tapecasting methods for makingthin films. In these methods, the ceramic powder is first dispersed in aliquid or solvent that contains a dissolved binder and optionallydispersing agents to from a homogeneous mixture. This homogeneousmixture or “slip” is then cast using the doctor blade casting methodonto a substrate. In some examples, the substrate is a non-sticksubstrate such as, but not limited to, silicone coated MYLAR. Then theliquid or solvent is evaporated to form a dried “green film.” In someexamples, the green film is peeled off the MYLAR and cut into a specificshape, e.g., square, rectangular, circular, or oval. In this methods,films having a thickness of 0.1 to 200 μm are prepared. Metal powderscan optionally be incorporated into the film or adhered to one side ofthe film. In these examples, the metal powders are selected from Ni, Cu,a mixture of Ni-garnet, a mixture of Cu-garnet, or combinations thereof.In some examples, tape casting includes using an opening of about 1-100μm through which the tape casting occurs during deposition.

iii. Hot Pressing

In some examples, set forth herein are hot pressing methods of makingthin garnet films. In these examples, green tapes, as described above,are sintered under an applied uniaxial pressure as shown in FIG. 4. Incertain examples, the binder is first removed before the sintering isconducted. In these particular examples, the binder can be removed byburning the binder at a temperature of about 200, 300, 400, 500, or 600°C. In some examples, the sintering is conducted by heating the film tosintering temperature of about 800° C. to about 1200° C. under anuniaxial load pressure of about 10 to about 100 MPa. In these examples,the applied pressure prevents the film from deforming or warping duringsintering and provides an additional driving force for sintering in thedirection perpendicular to the film surface and for preparing a densefilm.

In some examples, the green film can be sintered by first casting thefilm onto a metal foil. In some examples, the binder is burned outbefore the sintering is conducted. In some of these examples, thesintering includes heating the film under an applied pressure to atemperature lower than the melting point of the metal or metalscomprising the metal foil substrate. As such, higher sinteringtemperatures can be used when Ni-substrates are used as compared to whenCu-substrates are used.

iv. Constrained Sintering

In some examples, the green film may be sintered by placing it betweensetter plates but only applied a small amount of pressure to constrainthe film and prevent inhomogeneities that stress and warp the filmduring the sintering process. In some of these examples, it isbeneficial to make the setter plates that are porous, e.g., porousyttria-stabilized zirconia. These porous plates in these examples allowthe binder to diffuse away from the film during the burning out or thesintering step. In some of these examples, the burning out and sinteringstep can be accomplished simultaneously in part because of these poroussetter plates. In some examples, the small amount of pressure is justthe pressure applied by the weight of the setter plate resting on top ofthe green film during the sintering process with no additional pressureapplied externally. In some examples, the constrained sintering is donesubstantially as shown in FIG. 4 and, or, FIG. 5.

v. Vacuum Sintering

In some examples, the sintering is conducted as described above but withthe sintering film in a vacuum chamber. In this example, a vacuum isprovided to withdraw gases trapped within the ceramic that is sintering.In some of these examples, gases trapped within the ceramic prevent theceramic from further sintering by applying a pressure within pore spaceswhich can be prevent the sintering ceramic from densifying beyond acertain point. By removing trapped gases using a vacuum system, poresthat did contain gas can be sintered and densified more so than theycould if the vacuum system did not withdraw the trapped gases.

vi. Field Assisted, Flash, and Fast Sintering

The field assisted sintering technique (FAST) sintering is capable ofenhancing sintering kinetics. The application of a field will moveelectrons, holes, and/or ions in the sintering material, which then heatthe material via Joule heating. The heating is focused at spots whereresistance is highest (P=I²R, wherein I is current, and R is resistance)which tend to be at the particle-particle necks. These spots areprecisely where sintering is desired, so FAST sintering can beespecially effective. A standard garnet sintering procedure can, in someexamples, take 6-36 hours at 1050-1200° C. In contrast, FAST sinteringof garnets can occur at 600° C. and less than 5 minutes. The advantagesare lower cost processing (higher throughput), lower reactivity (atlower temperature, the garnet is less likely to react with othercomponents), and lower lithium loss (lithium evaporation is a dominantfailure mode preventing effective sintering). FAST sintering of garnetsis most effective at low current and for short time [insert data]. Sincegarnet material has high ion conductivity, low current is preferable, asis AC current, so that bulk transport of ions does not occur. Parametersmay span: 1 min<time<1 hr, 500<temp<1050° C., 1 Hz<frequency<1 MHz,1V<VAC rms<20V. In some examples, FAST sintering is used in conjunctionwith hot pressing, which includes applying a uniaxial pressure to thefilm during sintering. In some examples, FAST sintering is used inconjunction with hot pressing onto a permanent substrate, such as ametal, e.g., a current collector. In some examples, FAST sintering isused in conjunction with constrained sintering, in which the film ispinned, or constrained physically, but without a significant amount ofpressure. In some examples, FAST sintering is used in conjunction withbilayer sintering (and tri-layer sintering, e.g.,electrolyte-metal-electrolyte), to both provide mechanical support andto simultaneously form a current collector in one step. In someexamples, FAST sintering is used in conjunction with vacuum sintering,in which sintering occurs in a low absolute pressure to promote poreremoval.

In some embodiments, disclosed herein is a method of making thin films,including providing an unsintered thin film; wherein the unsintered thinfilm includes at least one member selected from the group consisting ofa Garnet-type electrolyte, an active electrode material, a conductiveadditive, a solvent, a binder, and combinations thereof. In someexamples, the methods further include removing the solvent, if presentin the unsintered thin film. In some examples, the method optionallyincludes laminating the film to a surface. In some examples, the methodincludes removing the binder, if present in the film. In some examples,the method includes sintering the film, wherein sintering comprises heatsintering or field assisted sintering (FAST). In some of these examples,heat sintering includes heating the film in the range from about 700° C.to about 1200° C. for about 1 to about 600 minutes and in atmospherehaving an oxygen partial pressure in the range 1*10⁻¹ to 1*10⁻⁵ atm. Inother examples, FAST sintering includes heating the film in the rangefrom about 500° C. to about 900° C. and applying a D.C. or A.C. electricfield to the thin film.

In some embodiments, disclosed herein is a method of making a film,including providing an unsintered thin film; wherein the unsintered thinfilm includes at least one member selected from the group consisting ofa Garnet-type electrolyte, an active electrode (e.g., cathode) material,a conductive additive, a solvent, a binder, and combinations thereof. Insome examples, the methods further include removing the solvent, ifpresent in the unsintered thin film. In some examples, the methodoptionally includes laminating the film to a surface. In some examples,the method includes removing the binder, if present in the film. In someexamples, the method includes sintering the film, wherein sinteringcomprises heat sintering. In some of these examples, heat sinteringincludes heating the film in the range from about 700° C. to about 1200°C. for about 1 to about 600 minutes and in atmosphere having an oxygenpartial pressure in the range of 1*10¹ atm to 1*10⁻¹⁵ atm.

In some embodiments, disclosed herein is a method of making a film,including providing an unsintered thin film; wherein the unsintered thinfilm includes at least one member selected from the group consisting ofa Garnet-type electrolyte, an active electrode material, a conductiveadditive, a solvent, a binder, and combinations thereof. In someexamples, the methods further include removing the solvent, if presentin the unsintered thin film. In some examples, the method optionallyincludes laminating the film to a surface. In some examples, the methodincludes removing the binder, if present in the film. In some examples,the method includes sintering the film, wherein sintering includes fieldassisted sintering (FAST). In some of these examples, FAST sinteringincludes heating the film in the range from about 500° C. to about 900°C. and applying a D.C. or A.C. electric field to the thin film.

In any of the methods set forth herein, the unsintered thin film mayinclude a lithium stuffed garnet electrolyte or precursors thereto. Inany of the methods set forth herein, the unsintered thin film mayinclude a lithium stuffed garnet electrolyte doped with alumina.

In any of the methods set forth herein, heat sintering may includeheating the film in the range from about 400° C. to about 1200° C.; orabout 500° C. to about 1200° C.; or about 900° C. to about 1200° C.; orabout 1000° C. to about 1200° C.; or about 1100° C. to about 1200° C.

In any of the methods set forth herein, the methods may include heatingthe film for about 1 to about 600 minutes. In any of the methods setforth herein, the methods may include heating the film for about 20 toabout 600 minutes. In any of the methods set forth herein, the methodsmay include heating the film for about 30 to about 600 minutes. In anyof the methods set forth herein, the methods may include heating thefilm for about 40 to about 600 minutes. In any of the methods set forthherein, the methods may include heating the film for about 50 to about600 minutes. In any of the methods set forth herein, the methods mayinclude heating the film for about 60 to about 600 minutes. In any ofthe methods set forth herein, the methods may include heating the filmfor about 70 to about 600 minutes. In any of the methods set forthherein, the methods may include heating the film for about 80 to about600 minutes. In any of the methods set forth herein, the methods mayinclude heating the film for about 90 to about 600 minutes. In any ofthe methods set forth herein, the methods may include heating the filmfor about 100 to about 600 minutes. In any of the methods set forthherein, the methods may include heating the film for about 120 to about600 minutes. In any of the methods set forth herein, the methods mayinclude heating the film for about 140 to about 600 minutes. In any ofthe methods set forth herein, the methods may include heating the filmfor about 160 to about 600 minutes. In any of the methods set forthherein, the methods may include heating the film for about 180 to about600 minutes. In any of the methods set forth herein, the methods mayinclude heating the film for about 200 to about 600 minutes. In any ofthe methods set forth herein, the methods may include heating the filmfor about 300 to about 600 minutes. In any of the methods set forthherein, the methods may include heating the film for about 350 to about600 minutes. In any of the methods set forth herein, the methods mayinclude heating the film for about 400 to about 600 minutes. In any ofthe methods set forth herein, the methods may include heating the filmfor about 450 to about 600 minutes. In any of the methods set forthherein, the methods may include heating the film for about 500 to about600 minutes. In any of the methods set forth herein, the methods mayinclude heating the film for about 1 to about 500 minutes. In any of themethods set forth herein, the methods may include heating the film forabout 1 to about 400 minutes. In any of the methods set forth herein,the methods may include heating the film for about 1 to about 300minutes. In any of the methods set forth herein, the methods may includeheating the film for about 1 to about 200 minutes. In any of the methodsset forth herein, the methods may include heating the film for about 1to about 100 minutes. In any of the methods set forth herein, themethods may include heating the film for about 1 to about 50 minutes.

In any of the methods set forth herein, the FAST sintering may includeheating the film in the range from about 400° C. to about 1200° C. andapplying a D.C. or A.C. electric field to the thin film. In someexamples, FAST sintering includes heating the film in the range fromabout 400° C. to about 900° C. and applying a D.C. or A.C. electricfield to the thin film. In some examples, FAST sintering includesheating the film in the range from about 600° C. to about 1150° C. andapplying a D.C. or A.C. electric field to the thin film. In someexamples, FAST sintering includes heating the film in the range fromabout 700° C. to about 900° C. and applying a D.C. or A.C. electricfield to the thin film. In some examples, FAST sintering includesheating the film in the range from about 800° C. to about 900° C. andapplying a D.C. or A.C. electric field to the thin film. In someexamples, FAST sintering includes heating the film in the range fromabout 500° C. to about 800° C. and applying a D.C. or A.C. electricfield to the thin film. In some examples, FAST sintering includesheating the film in the range from about 500° C. to about 700° C. andapplying a D.C. or A.C. electric field to the thin film. In someexamples, FAST sintering includes heating the film in the range fromabout 500° C. to about 600° C. and applying a D.C. or A.C. electricfield to the thin film.

In any of the methods set forth herein, the FAST sintering may includeheating the film in the range from about 400° C. to about 1000° C. andapplying a D.C. electric field to the thin film. In some examples, FASTsintering includes heating the film in the range from about 600° C. toabout 900° C. and applying a D.C. electric field to the thin film. Insome examples, FAST sintering includes heating the film in the rangefrom about 600° C. to about 900° C. and applying a D.C. electric fieldto the thin film. In some examples, FAST sintering includes heating thefilm in the range from about 700° C. to about 900° C. and applying aD.C. electric field to the thin film. In some examples, FAST sinteringincludes heating the film in the range from about 800° C. to about 900°C. and applying a D.C. electric field to the thin film. In someexamples, FAST sintering includes heating the film in the range fromabout 500° C. to about 800° C. and applying a D.C. electric field to thethin film. In some examples, FAST sintering includes heating the film inthe range from about 500° C. to about 700° C. and applying a D.C.electric field to the thin film. In some examples, FAST sinteringincludes heating the film in the range from about 500° C. to about 600°C. and applying a D.C. electric field to the thin film.

In any of the methods set forth herein, the FAST sintering may includeheating the film in the range from about 400° C. to about 1000° C. andapplying an A.C. electric field to the thin film. In any of the methodsset forth herein, the FAST sintering may include heating the film in therange from about 500° C. to about 900° C. and applying an A.C. electricfield to the thin film. In some examples, FAST sintering includesheating the film in the range from about 600° C. to about 900° C. andapplying an A.C. electric field to the thin film. In some examples, FASTsintering includes heating the film in the range from about 700° C. toabout 900° C. and applying an A.C. electric field to the thin film. Insome examples, FAST sintering includes heating the film in the rangefrom about 800° C. to about 900° C. and applying an A.C. electric fieldto the thin film. In some examples, FAST sintering includes heating thefilm in the range from about 500° C. to about 800° C. and applying anA.C. electric field to the thin film. In some examples, FAST sinteringincludes heating the film in the range from about 500° C. to about 700°C. and applying an A.C. electric field to the thin film. In someexamples, FAST sintering includes heating the film in the range fromabout 500° C. to about 600° C. and applying an A.C. electric field tothe thin film.

In certain examples, the methods set forth herein include providing anunsintered thin film by casting a film according to a casting methodsset forth in the instant disclosure.

In some of the methods disclosed herein, the sintering occurs betweeninert setter plates. In some examples, when the sintering occurs betweeninert setter plates, a pressure is applied by the setter plates onto thesintering film. In certain examples, the pressure is between 1 and 1000pounds per square inch (PSI). In some examples, the pressure is 1 PSI.In other examples, the pressure is 10 PSI. In still others, the pressureis 20 PSI. In some other examples, the pressure is 30 PSI. In certainexamples, the pressure is 40 PSI. In yet other examples, the pressure is50 PSI. In some examples, the pressure is 60 PSI. In yet other examples,the pressure is 70 PSI. In certain examples, the pressure is 80 PSI. Inother examples, the pressure is 90 PSI. In yet other examples, thepressure is 100 PSI. In some examples, the pressure is 110 PSI. In otherexamples, the pressure is 120 PSI. In still others, the pressure is 130PSI. In some other examples, the pressure is 140 PSI. In certainexamples, the pressure is 150 PSI. In yet other examples, the pressureis 160 PSI. In some examples, the pressure is 170 PSI. In yet otherexamples, the pressure is 180 PSI. In certain examples, the pressure is190 PSI. In other examples, the pressure is 200 PSI. In yet otherexamples, the pressure is 210 PSI.

In some of the above examples, the pressure is 220 PSI. In otherexamples, the pressure is 230 PSI. In still others, the pressure is 240PSI. In some other examples, the pressure is 250 PSI. In certainexamples, the pressure is 260 PSI. In yet other examples, the pressureis 270 PSI. In some examples, the pressure is 280 PSI. In yet otherexamples, the pressure is 290 PSI. In certain examples, the pressure is300 PSI. In other examples, the pressure is 310 PSI. In yet otherexamples, the pressure is 320 PSI. In some examples, the pressure is 330PSI. In other examples, the pressure is 340 PSI. In still others, thepressure is 350 PSI. In some other examples, the pressure is 360 PSI. Incertain examples, the pressure is 370 PSI. In yet other examples, thepressure is 380 PSI. In some examples, the pressure is 390 PSI. In yetother examples, the pressure is 400 PSI. In certain examples, thepressure is 410 PSI. In other examples, the pressure is 420 PSI. In yetother examples, the pressure is 430 PSI. In some other examples, thepressure is 440 PSI. In certain examples, the pressure is 450 PSI. Inyet other examples, the pressure is 460 PSI. In some examples, thepressure is 470 PSI. In yet other examples, the pressure is 480 PSI. Incertain examples, the pressure is 490 PSI. In other examples, thepressure is 500 PSI. In yet other examples, the pressure is 510 PSI.

In some of the above examples, the pressure is 520 PSI. In otherexamples, the pressure is 530 PSI. In still others, the pressure is 540PSI. In some other examples, the pressure is 550 PSI. In certainexamples, the pressure is 560 PSI. In yet other examples, the pressureis 570 PSI. In some examples, the pressure is 580 PSI. In yet otherexamples, the pressure is 590 PSI. In certain examples, the pressure is600 PSI. In other examples, the pressure is 610 PSI. In yet otherexamples, the pressure is 620 PSI. In some examples, the pressure is 630PSI. In other examples, the pressure is 640 PSI. In still others, thepressure is 650 PSI. In some other examples, the pressure is 660 PSI. Incertain examples, the pressure is 670 PSI. In yet other examples, thepressure is 680 PSI. In some examples, the pressure is 690 PSI. In yetother examples, the pressure is 700 PSI. In certain examples, thepressure is 710 PSI. In other examples, the pressure is 720 PSI. In yetother examples, the pressure is 730 PSI. In some other examples, thepressure is 740 PSI. In certain examples, the pressure is 750 PSI. Inyet other examples, the pressure is 760 PSI. In some examples, thepressure is 770 PSI. In yet other examples, the pressure is 780 PSI. Incertain examples, the pressure is 790 PSI. In other examples, thepressure is 800 PSI. In yet other examples, the pressure is 810 PSI.

In other examples, the pressure is 820 PSI. In certain aforementionedexamples, the pressure is 830 PSI. In still others, the pressure is 840PSI. In some other examples, the pressure is 850 PSI. In certainexamples, the pressure is 860 PSI. In yet other examples, the pressureis 870 PSI. In some examples, the pressure is 880 PSI. In yet otherexamples, the pressure is 890 PSI. In certain examples, the pressure is900 PSI. In other examples, the pressure is 910 PSI. In yet otherexamples, the pressure is 920 PSI. In some examples, the pressure is 930PSI. In other examples, the pressure is 940 PSI. In still others, thepressure is 950 PSI. In some other examples, the pressure is 960 PSI. Incertain examples, the pressure is 970 PSI. In yet other examples, thepressure is 980 PSI. In some examples, the pressure is 990 PSI. In yetother examples, the pressure is 1000 PSI.

In some examples, the setter plates can be porous. In some otherexamples, the setter plates are not porous. In some examples, thelithium activity in the setter plates is relatively high, that is, thelithium concentration is at least 10 atomic percent of the setter. Inother instance, the setter plates may be made of a garnet materialdescribed herein. In some examples, the setter plates can be porousgarnet setter plates. In other instance, the setter plates may be madeof zirconia. In some examples, the setter plates can be porous zirconiasetter plates. In other instance, the setter plates may be made of ametal material described herein. In some examples, the setter plates canbe porous metal setter plates.

In some examples, the garnet-based setter plates are useful forimparting beneficial surface properties to the sintered film. Thesebeneficial surface properties include flatness and conductivity usefulfor battery applications. These beneficial properties also includepreventing Li evaporation during sintering. These beneficial propertiesmay also include preferencing a particular garnet crystal structure. Incertain methods disclosed herein, the inert setter plates are selectedfrom porous zirconia, graphite or conductive metal plates. In some otherof these methods, the inert setter plates are graphite. In yet othermethods, the inert setter plates are conductive metal plates.

In some of the methods disclosed herein, FAST sintering includesoperating in a constant voltage amplitude mode and thereafter operatingin a constant current amplitude mode once the impedance of the filmdecreases by at least an order of magnitude.

In some of the methods disclosed herein, FAST sintering includesoperating in a constant voltage amplitude mode and thereafter operatingin a constant current amplitude mode once the impedance of the sinteredfilms decreases by an order of magnitude.

In some of the methods disclosed herein, FAST sintering includesoperating in a constant voltage amplitude mode and thereafter operatingin a constant current amplitude mode once the impedance of the sinteredfilms decreases by two orders of magnitude.

In some of the methods disclosed herein, FAST sintering includesoperating in a constant voltage amplitude mode and thereafter operatingin a constant current amplitude mode once the impedance of the sinteredfilms decreases by three orders of magnitude.

in some of the methods disclosed herein, FAST sintering includesoperating in a constant voltage amplitude mode and thereafter operatingin a constant current amplitude mode once the impedance of the sinteredfilms decreases by four orders of magnitude.

In some of the methods disclosed herein, FAST sintering includesoperating in a constant voltage amplitude mode and thereafter operatingin a constant current amplitude mode once the impedance of the sinteredfilms decreases from 1-100 MegaOhm-cm to about 1-10,000 Ohm-cm.

In some of the methods disclosed herein, FAST sintering includesoperating in a constant voltage until the Garnet-particles have a mediandimension that is double compared to the Garnet-particles beforesintering occurs.

In some of the methods disclosed herein, FAST sintering includesoperating a constant power until the Garnet-particles have a mediandimension that is double compared to the Garnet-particles beforesintering occurs.

In some of the methods disclosed herein, FAST sintering includesoperating in a constant current until the Garnet-particles have a mediandimension that is double compared to the Garnet-particles beforesintering occurs.

In some of the methods disclosed herein. FAST sintering includesoperating in a constant voltage until the film has a density of this isat least 20, 30, 40, or 50% greater than the film before sinteringoccurs. In some of the methods disclosed herein, FAST sintering includesoperating a constant power until the film has a density at least 20, 30,40, or 50% greater than the film before sintering occurs. In some of themethods disclosed herein, FAST sintering includes operating in aconstant current until the film has a density at least 20, 30, 40, or50% greater than the film before sintering occurs.

In some of the methods disclosed herein, FAST sintering includesoperating in a constant voltage until the film has an impedance that isat least 1, 2, 3, or 4 orders of magnitude lower than the film hasbefore sintering occurs. In some of the methods disclosed herein. FASTsintering includes operating a constant power until the film has animpedance that is at least 1, 2, 3, or 4 orders of magnitude lower thanthe film has before sintering occurs. In some of the methods disclosedherein, FAST sintering includes operating in a constant current untilthe film has an impedance of that is at least 1, 2, 3, or 4 orders ofmagnitude lower than the film has before sintering occurs.

In some of the methods disclosed herein, FAST sintering includesoperating in a constant voltage until the film has an impedance that isat least 1 or at most 10 orders of magnitude lower than the film hasbefore sintering occurs. In some of the methods disclosed herein, FASTsintering includes operating a constant power until the film has animpedance that is at least 1 or at most 10 orders of magnitude lowerthan the film has before sintering occurs. In some of the methodsdisclosed herein, FAST sintering includes operating in a constantcurrent until the film has an impedance that is at least 1 or at most 10orders of magnitude lower than the film has before sintering occurs.

In some of the methods disclosed herein, FAST sintering includesoperating in a constant voltage until the film has an impedance that isabout 2 orders of magnitude lower than the film has before sinteringoccurs. In some of the methods disclosed herein, FAST sintering includesoperating a constant power until the film has an impedance that is about2 orders of magnitude lower than the film has before sintering occurs.In some of the methods disclosed herein, FAST sintering includesoperating in a constant current until the film has an impedance that isat about 2 orders of magnitude lower than the film has before sinteringoccurs.

In some of the methods disclosed herein, FAST sintering includesoperating in a constant voltage until the film has an impedance that isabout 6 orders of magnitude lower than the film has before sinteringoccurs. In some of the methods disclosed herein, FAST sintering includesoperating a constant power until the film has an impedance that is about6 orders of magnitude lower than the film has before sintering occurs.In some of the methods disclosed herein, FAST sintering includesoperating in a constant current until the film has an impedance that isat about 6 orders of magnitude lower than the film has before sinteringoccurs.

In some of the methods disclosed herein, FAST sintering includesoperating in a constant voltage. In some of the methods disclosedherein. FAST sintering includes operating a constant power. In some ofthe methods disclosed herein. FAST sintering includes operating in aconstant current.

In some of the methods disclosed herein, FAST sintering includesoperating in a constant voltage amplitude mode and thereafter operatingin a constant current amplitude mode once the impedance of the filmdecreases by at least an order of magnitude.

In some of the methods disclosed herein, FAST sintering includesoperating in a ramped voltage until the Garnet-particles have a mediandimension that is at least two times that of the Garnet-particles beforesintering occurs. In some of the methods disclosed herein, FASTsintering includes operating a ramped power until the Garnet-particleshave a median dimension that is at least two times that of theGarnet-particles before sintering occurs. In some of the methodsdisclosed herein, FAST sintering includes operating in a ramped currentuntil the Garnet-particles have a median dimension that is at least twotimes that of the Garnet-particles before sintering occurs.

In some embodiments, FAST sintering is operated with feedback controlwherein the applied voltage, power, or current are adjusted duringsintering to meet certain pre-determined values. In some examples, thesevalues include the thickness of the film. For example, in some examplessintering is applied until the film is 50 μm thick. In other examples,the sintering is applied until the film is 40 μm thick. In otherexamples, the sintering is applied until the film is 30 μm thick. Inother examples, the sintering is applied until the film is 20 μm thick.In other examples, the sintering is applied until the film is 10 μmthick. In other examples, the sintering is applied until the film is 5μm thick. In other examples, the sintering is applied until the film is1 μm thick. In other examples, the sintering is applied until the filmis 0.5 μm thick. As used in this paragraph, thickness refers to theaverage dimensions of the film in the z-direction (as shown in FIG. 23.

In some embodiments, FAST sintering is operated with feedback controlwherein the applied voltage, power, or current are adjusted duringsintering to meet certain pre-determined values. In some examples, thesevalues include the conductivity of the film. For example, the sinteringcan be applied until the film has a conductivity of 1e-4 S/cm. In otherexamples, the sintering can be applied until the film has a conductivityof 1e-5 S/cm. In other examples, the sintering can be applied until thefilm has a conductivity of 1e-6S/cm. In other examples, the sinteringcan be applied until the film has a conductivity of 1e-7S/cm. In otherexamples, the sintering can be applied until the film has a conductivityof 1e-8S/cm.

In some embodiments. FAST sintering is operated with feedback controlwherein the applied voltage, power, or current are adjusted duringsintering to meet certain pre-determined values. In some examples, thesevalues include the impedance of the film. For example, sintering can beapplied until the impedance of the film is 500 Ohm-cm.

In some embodiments, FAST sintering is operated with feedback controlwherein the applied voltage, power, or current are adjusted duringsintering to meet certain pre-determined values. In some examples, thesevalues include the particle size in the film.

In some embodiments, FAST sintering is operated with feedback controlwherein the applied voltage, power, or current are adjusted duringsintering to meet certain pre-determined values. In some examples, thesevalues include the density of the film.

In some embodiments, FAST sintering is operated with feedback controlwherein the applied voltage, power, or current are adjusted duringsintering to meet certain pre-determined values. In some examples, thesevalues include the optical density of the film.

In some embodiments, FAST sintering is operated with feedback controlwherein the applied voltage, power, or current are adjusted duringsintering to meet certain pre-determined values. In some examples, thesevalues include the temperature of the film. For example, the sinteringcan be applied until the film has a temperature of 50° C. In otherexamples, the sintering can be applied until the film has a temperatureof 100° C. In other examples, the sintering can be applied until thefilm has a temperature of 150° C. In other examples, the sintering canbe applied until the film has a temperature of 200° C. In otherexamples, the sintering can be applied until the film has a temperatureof 250° C. In other examples, the sintering can be applied until thefilm has a temperature of 300° C. In other examples, the sintering canbe applied until the film has a temperature of 350° C. In otherexamples, the sintering can be applied until the film has a temperatureof 400° C. In other examples, the sintering can be applied until thefilm has a temperature of 450° C. In other examples, the sintering canbe applied until the film has a temperature of 500° C. In otherexamples, the sintering can be applied until the film has a temperatureof 550° C. In other examples, the sintering can be applied until thefilm has a temperature of 600° C. In other examples, the sintering canbe applied until the film has a temperature of 650° C. In otherexamples, the sintering can be applied until the film has a temperatureof 700° C. In other examples, the sintering can be applied until thefilm has a temperature of 750° C. In other examples, the sintering canbe applied until the film has a temperature of 800° C. In otherexamples, the sintering can be applied until the film has a temperatureof 850° C. In other examples, the sintering can be applied until thefilm has a temperature of 900° C. In other examples, the sintering canbe applied until the film has a temperature of 950° C. In otherexamples, the sintering can be applied until the film has a temperatureof 1000° C. In other examples, the sintering can be applied until thefilm has a temperature of 1150° C. In other examples, the sintering canbe applied until the film has a temperature of 1200° C. In otherexamples, the sintering can be applied until the film has a temperatureof 1250° C. In other examples, the sintering can be applied until thefilm has a temperature of 1300° C. In other examples, the sintering canbe applied until the film has a temperature of 1350° C.

In some of the methods disclosed herein, FAST sintering includesoperating in a ramped voltage until the film has a density at least 20,30, 40, or 50% greater than the film before sintering occurs. In some ofthe methods disclosed herein, FAST sintering includes operating a rampedpower until the film has a density at least 20, 30, 40, or 50% greaterthan the film before sintering occurs. In some of the methods disclosedherein, FAST sintering includes operating in a ramped current until thefilm has a density of at least 20, 30, 40, or 50% greater than the filmbefore sintering occurs. In some of the methods disclosed herein, FASTsintering includes operating in a ramped voltage until the film has animpedance that is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 orders of magnitudelower than the film has before sintering occurs. In some of the methodsdisclosed herein, FAST sintering includes operating a ramped power untilthe film has an impedance that is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10orders of magnitude lower than the film has before sintering occurs. Insome of the methods disclosed herein, FAST sintering includes operatingin a ramped current until the film has an impedance that is 1, 2, 3, 4,5, 6, 7, 8, 9, or 10 orders of magnitude lower than the film has beforesintering occurs.

In some of the methods disclosed herein, FAST sintering includesoperating in a ramped voltage. In some of the methods disclosed herein.FAST sintering includes operating a ramped power. In some of the methodsdisclosed herein, FAST sintering includes operating in a ramped current.

In some of the methods disclosed herein, FAST sintering includesoperating in a constant voltage amplitude mode and thereafter operatingin a constant current amplitude mode once the impedance of the filmdecreases by at least an order of magnitude. In some of the methodsdisclosed herein, FAST sintering includes operating in a constantvoltage amplitude mode and thereafter operating in a constant currentamplitude mode once the impedance of the sintered films decreases by anorder of magnitude. In some of the methods disclosed herein, FASTsintering includes operating in a constant voltage amplitude mode andthereafter operating in a constant current amplitude mode once theimpedance of the sintered films decreases by two orders of magnitude. Insome of the methods disclosed herein, FAST sintering includes operatingin a constant voltage amplitude mode and thereafter operating in aconstant current amplitude mode once the impedance of the sintered filmsdecreases by three orders of magnitude. In some of the methods disclosedherein, FAST sintering includes operating in a constant voltageamplitude mode and thereafter operating in a constant current amplitudemode once the impedance of the sintered films decreases by four ordersof magnitude.

In some of the methods disclosed herein, FAST sintering includesoperating in a constant voltage amplitude mode and thereafter operatingin a constant current amplitude mode once the impedance of the sinteredfilms decreases from 1-100 MegaOhm-cm to about 1-10,000 Ohm-cm.

In some of the methods disclosed herein, FAST sintering includesoperating in a constant voltage until the Garnet-particles have a mediandimension that is double compared to the Garnet-particles beforesintering occurs.

In some of the methods disclosed herein, FAST sintering includesoperating a constant power until the Garnet-particles have a mediandimension that is double compared to the Garnet-particles beforesintering occurs.

In some of the methods disclosed herein, FAST sintering includesoperating in a constant current until the Garnet-particles have a mediandimension that is double compared to the Garnet-particles beforesintering occurs.

In some of the methods disclosed herein, FAST sintering includesoperating in a constant voltage until the film has a density of this isat least 20, 30, 40, or 50% greater than the film before sinteringoccurs. In some of the methods disclosed herein. FAST sintering includesoperating a constant power until the film has a density at least 20, 30,40, or 50% greater than the film before sintering occurs. In some of themethods disclosed herein, FAST sintering includes operating in aconstant current until the film has a density at least 20, 30, 40, or50% greater than the film before sintering occurs.

In some of the methods disclosed herein, FAST sintering includesoperating in a constant voltage until the film has an impedance that isat least 1, 2, 3, or 4 orders of magnitude lower than the film hasbefore sintering occurs. In some of the methods disclosed herein, FASTsintering includes operating a constant power until the film has animpedance that is at least 1, 2, 3, or 4 orders of magnitude lower thanthe film has before sintering occurs. In some of the methods disclosedherein, FAST sintering includes operating in a constant current untilthe film has an impedance of that is at least 1, 2, 3, or 4 orders ofmagnitude lower than the film has before sintering occurs.

In some of the methods disclosed herein, FAST sintering includesoperating in a constant voltage until the film has an impedance that isat least 1 or at most 10 orders of magnitude lower than the film hasbefore sintering occurs. In some of the methods disclosed herein, FASTsintering includes operating a constant power until the film has animpedance that is at least 1 or at most 10 orders of magnitude lowerthan the film has before sintering occurs. In some of the methodsdisclosed herein, FAST sintering includes operating in a constantcurrent until the film has an impedance that is at least 1 or at most 10orders of magnitude lower than the film has before sintering occurs.

In some of the methods disclosed herein, FAST sintering includesoperating in a constant voltage until the film has an impedance that isabout 2 orders of magnitude lower than the film has before sinteringoccurs. In some of the methods disclosed herein, FAST sintering includesoperating a constant power until the film has an impedance that is about2 orders of magnitude lower than the film has before sintering occurs.In some of the methods disclosed herein, FAST sintering includesoperating in a constant current until the film has an impedance that isat about 2 orders of magnitude lower than the film has before sinteringoccurs.

In some of the methods disclosed herein, FAST sintering includesoperating in a constant voltage until the film has an impedance that isabout 6 orders of magnitude lower than the film has before sinteringoccurs. In some of the methods disclosed herein, FAST sintering includesoperating a constant power until the film has an impedance that is about6 orders of magnitude lower than the film has before sintering occurs.In some of the methods disclosed herein. FAST sintering includesoperating in a constant current until the film has an impedance that isat about 6 orders of magnitude lower than the film has before sinteringoccurs.

In some of the methods disclosed herein, FAST sintering includesoperating in a constant voltage. In some of the methods disclosedherein, FAST sintering includes operating a constant power. In some ofthe methods disclosed herein, FAST sintering includes operating in aconstant current.

In some of the methods disclosed herein, FAST sintering includesoperating in a constant voltage amplitude mode and thereafter operatingin a constant current amplitude mode once the impedance of the filmdecreases by at least an order of magnitude.

In some of the methods disclosed herein, FAST sintering includesoperating in a ramped voltage until the Garnet-particles have a mediandimension that is at least two times that of the Garnet-particles beforesintering occurs. In some of the methods disclosed herein, FASTsintering includes operating a ramped power until the Garnet-particleshave a median, dimension that is at least two times that of theGarnet-particles before sintering occurs. In some of the methodsdisclosed herein, FAST sintering includes operating in a ramped currentuntil the Garnet-particles have a median dimension that is at least twotimes that of the Garnet-particles before sintering occurs.

In some embodiments, FAST sintering is operated with feedback controlwherein the applied voltage, power, or current are adjusted duringsintering to meet certain pre-determined values. In some examples, thesevalues include the thickness of the film. For example, in some examplessintering is applied until the film is 50 μm thick. In other examples,the sintering is applied until the film is 40 sun thick. In otherexamples, the sintering is applied until the film is 30 μm thick. Inother examples, the sintering is applied until the film is 20 μm thick.In other examples, the sintering is applied until the film is 10 μmthick. In other examples, the sintering is applied until the film is 5μm thick. In other examples, the sintering is applied until the film isI μm thick. In other examples, the sintering is applied until the filmis 0.5 μm thick. As used in this paragraph, thickness refers to theaverage dimensions of the film in the z-direction (as shown in FIG. 23.

In some embodiments, FAST sintering is operated with feedback controlwherein the applied voltage, power, or current are adjusted duringsintering to meet certain pre-determined values. In some examples, thesevalues include the conductivity of the film. For example, the sinteringcan be applied until the film has a conductivity of 1e-4 S/cm. In otherexamples, the sintering can be applied until the film has a conductivityof 1e-5 S/cm. In other examples, the sintering can be applied until thefilm has a conductivity of 1e-6S/cm. In other examples, the sinteringcan be applied until the film has a conductivity of 1e-7S/cm. In otherexamples, the sintering can be applied until the film has a conductivityof 1e-8S/cm.

In some embodiments, FAST sintering is operated with feedback controlwherein the applied voltage, power, or current are adjusted duringsintering to meet certain pre-determined values. In some examples, thesevalues include the impedance of the film. For example, sintering can beapplied until the impedance of the film is 500 Ohm-cm.

In some embodiments, FAST sintering is operated with feedback controlwherein the applied voltage, power, or current are adjusted duringsintering to meet certain pre-determined values. In some examples, thesevalues include the particle size in the film.

In some embodiments, FAST sintering is operated with feedback controlwherein the applied voltage, power, or current are adjusted duringsintering to meet certain pre-determined values. In some examples, thesevalues include the density of the film.

In some embodiments, FAST sintering is operated with feedback controlwherein the applied voltage, power, or current are adjusted duringsintering to meet certain pre-determined values. In some examples, thesevalues include the optical density of the film.

In some embodiments. FAST sintering is operated with feedback controlwherein the applied voltage, power, or current are adjusted duringsintering to meet certain pre-determined values. In some examples, thesevalues include the temperature of the film. For example, the sinteringcan be applied until the film has a temperature of 50° C. In otherexamples, the sintering can be applied until the film has a temperatureof 100° C. In other examples, the sintering can be applied until thefilm has a temperature of 150° C. In other examples, the sintering canbe applied until the film has a temperature of 200° C. In otherexamples, the sintering can be applied until the film has a temperatureof 250° C. In other examples, the sintering can be applied until thefilm has a temperature of 300° C. In other examples, the sintering canbe applied until the film has a temperature of 350° C. In otherexamples, the sintering can be applied until the film has a temperatureof 400° C. In other examples, the sintering can be applied until thefilm has a temperature of 450° C. In other examples, the sintering canbe applied until the film has a temperature of 500° C. In otherexamples, the sintering can be applied until the film has a temperatureof 550° C. In other examples, the sintering can be applied until thefilm has a temperature of 600° C. In other examples, the sintering canbe applied until the film has a temperature of 650° C. In otherexamples, the sintering can be applied until the film has a temperatureof 700° C. In other examples, the sintering can be applied until thefilm has a temperature of 750° C. In other examples, the sintering canbe applied until the film has a temperature of 800° C. In otherexamples, the sintering can be applied until the film has a temperatureof 850° C. In other examples, the sintering can be applied until thefilm has a temperature of 900° C. In other examples, the sintering canbe applied until the film has a temperature of 950° C. In otherexamples, the sintering can be applied until the film has a temperatureof 1000° C. In other examples, the sintering can be applied until thefilm has a temperature of 1150° C. In other example, the sintering canbe applied until the film has a temperature of 1200° C. In otherexamples, the sintering can be applied until the film has a temperatureof 1250° C. In other examples, the sintering can be applied until thefilm has a temperature of 1300° C. In other examples, the sintering canbe applied until the film has a temperature of 1350° C.

In some of the methods disclosed herein, FAST sintering includesoperating in a ramped voltage until the film has a density at least 20,30, 40, or 50% greater than the film before sintering occurs. In some ofthe methods disclosed herein, FAST sintering includes operating a rampedpower until the film has a density at least 20, 30, 40, or 50% greaterthan the film before sintering occurs. In some of the methods disclosedherein, FAST sintering includes operating in a ramped current until thefilm has a density of at least 20, 30, 40, or 50% greater than the filmbefore sintering occurs.

In some of the methods disclosed herein, FAST sintering includesoperating in a ramped voltage until the film has an impedance that is 1,2, 3, 4, 5, 6, 7, 8, 9, or 10 orders of magnitude lower than the filmhas before sintering occurs. In some of the methods disclosed herein,FAST sintering includes operating a ramped power until the film has animpedance that is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 orders of magnitudelower than the film has before sintering occurs.

In some of the methods disclosed herein, FAST sintering includesoperating in a ramped current until the film has an impedance that is 1,2, 3, 4, 5, 6, 7, 8, 9, or 10 orders of magnitude lower than the filmhas before sintering occurs.

In some of the methods disclosed herein, FAST sintering includesoperating in a ramped voltage. In some of the methods disclosed herein,FAST sintering includes operating a ramped power. In some of the methodsdisclosed herein, FAST sintering includes operating in a ramped current.

In any of the methods set forth herein, the FAST sintering may includeheating the film in the range from about 400° C. to about 1000° C. andapplying a D.C. or A.C. electric field to the thin film. In someexamples, FAST sintering includes heating the film in the range fromabout 500° C. to about 900° C. and applying a D.C. or A.C. electricfield to the thin film. In some examples, FAST sintering includesheating the film in the range from about 600° C. to about 900° C. andapplying a D.C. or A.C. electric field to the thin film. In someexamples, FAST sintering includes heating the film in the range fromabout 700° C. to about 900° C. and applying a D.C. or A.C. electricfield to the thin film. In some examples, FAST sintering includesheating the film in the range from about 800° C. to about 900° C. andapplying a D.C. or A.C. electric field to the thin film. In someexamples, FAST sintering includes heating the film in the range fromabout 500° C. to about 800° C. and applying a D.C. or A.C. electricfield to the thin film. In some examples, FAST sintering includesheating the film in the range from about 500° C. to about 700° C. andapplying a D.C. or A.C. electric field to the thin film. In someexamples, FAST sintering includes heating the film in the range fromabout 500° C. to about 600° C. and applying a D.C. or A.C. electricfield to the thin film.

In any of the methods set forth herein, the FAST sintering may includeheating the film in the range from about 400° C. to about 1000° C. andapplying a D.C. electric field to the thin film. In some examples, FASTsintering includes heating the film in the range from about 600° C. toabout 900° C. and applying a D.C. electric field to the thin film. Insome examples, FAST sintering includes heating the film in the rangefrom about 600° C. to about 900° C. and applying a D.C. electric fieldto the thin film. In some examples, FAST sintering includes heating thefilm in the range from about 700° C. to about 900° C. and applying aD.C. electric field to the thin film. In some examples, FAST sinteringincludes heating the film in the range from about 800° C. to about 900°C. and applying a D.C. electric field to the thin film. In someexamples, FAST sintering includes heating the film in the range fromabout 500° C. to about 800° C. and applying a D.C. electric field to thethin film. In some examples, FAST sintering includes heating the film inthe range from about 500° C. to about 700° C. and applying a D.C.electric field to the thin film. In some examples, FAST sinteringincludes heating the film in the range from about 500° C. to about 600°C. and applying a D.C. electric field to the thin film.

In any of the methods set forth herein, the FAST sintering may includeheating the film in the range from about 400° C. to about 1000° C. andapplying an A.C. electric field to the thin film. In any of the methodsset forth herein, the FAST sintering may include heating the film in therange from about 500° C. to about 900° C. and applying an A.C. electricfield to the thin film. In some examples, FAST sintering includesheating the film in the range from about 600° C. to about 900° C. andapplying an A.C. electric field to the thin film. In some examples, FASTsintering includes heating the film in the range from about 700° C. toabout 900° C. and applying an A.C. electric field to the thin film. Insome examples, FAST sintering includes heating the film in the rangefrom about 800° C. to about 900° C. and applying an A.C. electric fieldto the thin film. In some examples, FAST sintering includes heating thefilm in the range from about 500° C. to about 800° C. and applying anA.C. electric field to the thin film. In some examples, FAST sinteringincludes heating the film in the range from about 500° C. to about 700°C. and applying an A.C. electric field to the thin film. In someexamples, FAST sintering includes heating the film in the range fromabout 500° C. to about 600° C. and applying an A.C. electric field tothe thin film.

In certain examples, the methods set forth herein include providing anunsintered thin film by casting a film.

vii. Composites

In another embodiment, the disclosure sets forth herein a method formaking a composite electrochemical device, including the following stepsin any order: providing an anode layer including an anode currentcollector, providing a Garnet-type solid state electrolyte (SSE) layerin contact with at least one side of the anode layer and optionallysintering the SSE; providing a porous Garnet layer in contact with theSSE layer and optionally sintering the porous Garnet layer; optionallyinfiltrating the porous Garnet layer with at least one member selectedfrom the group consisting of carbon, a lithium conducting polymer, anactive cathode material, and combinations thereof; and providing acathode current collector layer in contact with the porous Garnet layer.

In some examples, set forth herein is a method for sintering a thin andfree standing garnet film, including the following steps, in any order:providing a green tape by casting a garnet slurry; wherein the slurrycomprises at least one member selected from the group consisting ofgarnet precursors, garnet, a binder, a solvent, a plasticizer, adispersant, and combinations thereof, sintering the green tape betweensetter plates; wherein the sintering is heat, spark plasma, or fieldassisted sintering; and wherein sintering optionally includes applyingpressure to the film with the setter plates.

In some of these aforementioned examples, the slurry includes milled andcalcined garnet. In some examples, the solid loading of the green tapeis at least 30% w/w. In some examples, the solid loading of the greentape is at least 40% w/w. In some examples, the solid loading of thegreen tape is at least 50% w/w. In some examples, the solid loading ofthe green tape is at least 60% w/w. In some examples, the solid loadingof the green tape is at least 70% w/w. In some of these examples, thefilm is sintered directly onto a metal. In certain examples, the metalis a metal powder or a metal foil. In some examples, the metal powder isbetween and in contact with one side of the green tape and one setterplate. In other examples, the metal powder layer is positioned betweenand in contact with two green tapes, and wherein the green tapes arebetween and in contact with the setter plates. In certain examples, themetal powder is Ni or Cu powder. In some of these examples, a source ofLi is placed in proximity of the sintered film during sintering. In somespecific examples, the setter plates are selected from YSZ, graphite,YSZ, Mg—SZ, zirconia, porous zirconia, SiO₂, SiO₂ sand, Al₂O₃, Al₂O₃powder, Al₂O paper, nickel, nickel powder, garnet, garnet powder, asacrificial garnet film, LiAlO₂, LiLaO₂, Li₂ZrO₃. In some examples, twodifferent setter plates are used. In some of these examples, a zirconiasetter plate contacts the metal powder. In some examples, a pressureapplied is between 0.001 MPa to 200 MPa.

viii. Bilayer and Trilayer Sintering

In some examples, the films which are sintered are provided as layers ofa garnet-electrolyte in contact with a metal layer which is then incontact with a garnet-electrolyte layer. A non-limiting example is shownin FIG. 4 or FIG. 29.

ix. Heat Sintering

In some embodiments, disclosed herein is a method of making an energystorage electrode, including providing an unsintered thin film; whereinthe unsintered thin film includes at least one member selected from thegroup consisting of a Garnet-type electrolyte, an active electrodematerial, a conductive additive, a solvent, a binder, and combinationsthereof. In some examples, the methods further include removing thesolvent, if present in the unsintered thin film. In some examples, themethod optionally includes laminating the film to a surface. In someexamples, the method includes removing the binder, if present in thefilm. In some examples, the method includes sintering the film, whereinsintering comprises heat sintering. In some of these examples, heatsintering includes heating the film in the range from about 700° C. toabout 1200° C. for about 1 to about 600 minutes and in atmosphere havingan oxygen partial pressure in the range of 1e-1 atm to 1e-15 atm.

In some embodiments, disclosed herein is a method of making an energystorage electrode, including providing an unsintered thin film; whereinthe unsintered thin film includes at least one member selected from thegroup consisting of a Garnet-type electrolyte, an active electrodematerial, a conductive additive, a solvent, a binder, and combinationsthereof. In some examples, the methods further include removing thesolvent, if present in the unsintered thin film. In some examples, themethod optionally includes laminating the film to a surface. In someexamples, the method includes removing the binder, if present in thefilm. In some examples, the method includes sintering the film, whereinsintering includes field assisted sintering (FAST). In some of theseexamples, FAST sintering includes heating the film in the range fromabout 500° C. to about 900° C. and applying a D.C. or A.C. electricfield to the thin film.

In any of the methods set forth herein, the unsintered thin film mayinclude a Garnet-type electrolyte. In other methods, the unsintered thinfilm may include an active electrode material. In still other methods,the unsintered thin film may include a conductive additive. In certainmethods, the unsintered thin film may include a solvent. In certainmethods, the unsintered thin film may include a binder.

In any of the methods set forth herein, heat sintering may includeheating the film in the range from about 700° C. to about 1200° C.; orabout 800° C. to about 1200° C.; or about 900° C. to about 1200° C.; orabout 1000° C. to about 1200° C.; or about 1100° C. to about 1200° C. Inany of the methods set forth herein, heat sintering can include heatingthe film in the range from about 700° C. to about 1100° C.; or about700° C. to about 1000° C.; or about 700° C. to about 900° C.; or about700° C. to about 800° C. In any of the methods set forth herein, heatsintering can include heating the film to about 700° C., about 750° C.,about 850° C., about 800° C., about 900° C., about 950° C., about 1000°C., about 1050° C., about 1100° C., about 1150° C., or about 1200° C. Inany of the methods set forth herein, heat sintering can include heatingthe film to 700° C., 750° C., 850° C., 800° C., 900° C., 950° C., 1000°C. 1050° C., 1100° C., 1150° C., or 1200° C. In any of the methods setforth herein, heat sintering can include heating the film to 700° C. Inany of the methods set forth herein, heat sintering can include heatingthe film to 750° C. In any of the methods set forth herein, heatsintering can include heating the film to 850° C. In any of the methodsset forth herein, heat sintering can include heating the film to 900° C.In any of the methods set forth herein, heat sintering can includeheating the film to 950° C. In any of the methods set forth herein, heatsintering can include heating the film to 1000° C. In any of the methodsset forth herein, heat sintering can include heating the film to 1050°C. In any of the methods set forth herein, heat sintering can includeheating the film to 1100° C. In any of the methods set forth herein,heat sintering can include heating the film to 1150° C. In any of themethods set forth herein, heat sintering can include heating the film to1200° C.

In any of the methods set forth herein, the methods may include heatingthe film for about 1 to about 600 minutes. In any of the methods setforth herein, the methods may include heating the film for about 20 toabout 600 minutes. In any of the methods set forth herein, the methodsmay include heating the film for about 30 to about 600 minutes. In anyof the methods set forth herein, the methods may include heating thefilm for about 40 to about 600 minutes. In any of the methods set forthherein, the methods may include heating the film for about 50 to about600 minutes. In any of the methods set forth herein, the methods mayinclude heating the film for about 60 to about 600 minutes. In any ofthe methods set forth herein, the methods may include heating the filmfor about 70 to about 600 minutes. In any of the methods set forthherein, the methods may include heating the film for about 80 to about600 minutes. In any of the methods set forth herein, the methods mayinclude heating the film for about 90 to about 600 minutes. In any ofthe methods set forth herein, the methods may include heating the filmfor about 100 to about 600 minutes. In any of the methods set forthherein, the methods may include heating the film for about 120 to about600 minutes. In any of the methods set forth herein, the methods mayinclude heating the film for about 140 to about 600 minutes. In any ofthe methods set forth herein, the methods may include heating the filmfor about 160 to about 600 minutes. In any of the methods set forthherein, the methods may include heating the film for about 180 to about600 minutes. In any of the methods set forth herein, the methods mayinclude heating the film for about 200 to about 600 minutes. In any ofthe methods set forth herein, the methods may include heating the filmfor about 300 to about 600 minutes. In any of the methods set forthherein, the methods may include heating the film for about 350 to about600 minutes. In any of the methods set forth herein, the methods mayinclude heating the film for about 400 to about 600 minutes. In any ofthe methods set forth herein, the methods may include heating the filmfor about 450 to about 600 minutes. In any of the methods set forthherein, the methods may include heating the film for about 500 to about600 minutes. In any of the methods set forth herein, the methods mayinclude heating the film for about 1 to about 500 minutes. In any of themethods set forth herein, the methods may include heating the film forabout 1 to about 400 minutes. In any of the methods set forth herein,the methods may include heating the film for about 1 to about 300minutes. In any of the methods set forth herein, the methods may includeheating the film for about 1 to about 200 minutes. In any of the methodsset forth herein, the methods may include heating the film for about 1to about 100 minutes. In any of the methods set forth herein, themethods may include heating the film for about 1 to about 50 minutes.

x. Laminating

In some of the methods set forth herein the laminating includes applyinga pressure less than 1000 pounds per square inch (PSI) and heating thefilm. In other embodiments, the laminating includes applying a pressureless than 750 pounds per square inch (PSI) and heating the film. In someother embodiments, laminating includes applying a pressure less than 700pounds per square inch (PSI) and heating the film. In other embodiments,the laminating includes applying a pressure less than 650 pounds persquare inch (PSI) and heating the film. In some other embodiments,laminating includes applying a pressure less than 600 pounds per squareinch (PSI) and heating the film. In other embodiments, the laminatingincludes applying a pressure less than 550 pounds per square inch (PSI)and heating the film. In some other embodiments, laminating includesapplying a pressure less than 500 pounds per square inch (PSI) andheating the film. In other embodiments, the laminating includes applyinga pressure less than 450 pounds per square inch (PSI) and heating thefilm. In some other embodiments, laminating includes applying a pressureless than 400 pounds per square inch (PSI) and heating the film. Inother embodiments, the laminating includes applying a pressure less than350 pounds per square inch (PSI) and heating the film. In some otherembodiments, laminating includes applying a pressure less than 300pounds per square inch (PSI) and heating the film. In other embodiments,the laminating includes applying a pressure less than 250 pounds persquare inch (PSI) and heating the film. In some other embodiments,laminating includes applying a pressure less than 200 pounds per squareinch (PSI) and heating the film. In other embodiments, the laminatingincludes applying a pressure less than 150 pounds per square inch (PSI)and heating the film.

In some other embodiments, laminating includes applying a pressure lessthan 100 pounds per square inch (PSI) and heating the film. In otherembodiments, the laminating includes applying a pressure less than 50pounds per square inch (PSI) and heating the film. In some otherembodiments, laminating includes applying a pressure less than 10 poundsper square inch (PSI) and heating the film. Some of the laminatingmethods set forth herein include heating the film is heated to about 80°C. Some of the laminating methods set forth herein include heating thefilm is heated to about 25° C. to about 180° C.

In some of the methods disclosed herein, the laminating step includeslaminating an unsintered thin film electrolyte to a composite electrode;wherein the composite electrode includes at least one member selectedfrom the group consisting of an electrolyte, an active electrodematerial, a conductive additive, and combinations thereof. In certain ofthese embodiments, the composite electrode includes an electrolyte. Incertain other of these embodiments, the composite electrode includes anactive electrode material. In some other of these embodiments, thecomposite electrode includes a conductive additive.

xi. Setter Plates

In some of the methods disclosed herein, the sintering occurs betweeninert setter plates. In some examples, when the sintering occurs betweeninert setter plates, a pressure is applied by the setter plates onto thesintering film. In certain examples, the pressure is between 1 and 1000pounds per square inch (PSI). In some examples, the pressure is 1 PSI.In other examples, the pressure is 10 PSI. In still others, the pressureis 20 PSI. In some other examples, the pressure is 30 PSI. In certainexamples, the pressure is 40 PSI. In yet other examples, the pressure is50 PSI. In some examples, the pressure is 60 PSI. In yet other examples,the pressure is 70 PSI. In certain examples, the pressure is 80 PSI. Inother examples, the pressure is 90 PSI. In yet other examples, thepressure is 100 PSI. In some examples, the pressure is 110 PSI. In otherexamples, the pressure is 120 PSI. In still others, the pressure is 130PSI. In some other examples, the pressure is 140 PSI. In certainexamples, the pressure is 150 PSI. In yet other examples, the pressureis 160 PSI. In some examples, the pressure is 170 PSI. In yet otherexamples, the pressure is 180 PSI. In certain examples, the pressure is190 PSI. In other examples, the pressure is 200 PSI. In yet otherexamples, the pressure is 210 PSI.

In some of the above examples, the pressure is 220 PSI. In otherexamples, the pressure is 230 PSI. In still others, the pressure is 240PSI. In some other examples, the pressure is 250 PSI. In certainexamples, the pressure is 260 PSI. In yet other examples, the pressureis 270 PSI. In some examples, the pressure is 280 PSI. In yet otherexamples, the pressure is 290 PSI. In certain examples, the pressure is300 PSI. In other examples, the pressure is 310 PSI. In yet otherexamples, the pressure is 320 PSI. In some examples, the pressure is 330PSI. In other examples, the pressure is 340 PSI. In still others, thepressure is 350 PSI. In some other examples, the pressure is 360 PSI. Incertain examples, the pressure is 370 PSI. In yet other examples, thepressure is 380 PSI. In some examples, the pressure is 390 PSI. In yetother examples, the pressure is 400 PSI. In certain examples, thepressure is 410 PSI. In other examples, the pressure is 420 PSI. In yetother examples, the pressure is 430 PSI. In some other examples, thepressure is 440 PSI. In certain examples, the pressure is 450 PSI. Inyet other examples, the pressure is 460 PSI. In some examples, thepressure is 470 PSI. In yet other examples, the pressure is 480 PSI. Incertain examples, the pressure is 490 PSI. In other examples, thepressure is 500 PSI. In yet other examples, the pressure is 510 PSI.

In some of the above examples, the pressure is 520 PSI. In otherexamples, the pressure is 530 PSI. In still others, the pressure is 540PSI. In some other examples, the pressure is 550 PSI. In certainexamples, the pressure is 560 PSI. In yet other examples, the pressureis 570 PSI. In some examples, the pressure is 580 PSI. In yet otherexamples, the pressure is 590 PSI. In certain examples, the pressure is600 PSI. In other examples, the pressure is 610 PSI. In yet otherexamples, the pressure is 620 PSI. In some examples, the pressure is 630PSI. In other examples, the pressure is 640 PSI. In still others, thepressure is 650 PSI. In some other examples, the pressure is 660 PSI. Incertain examples, the pressure is 670 PSI. In yet other examples, thepressure is 680 PSI. In some examples, the pressure is 690 PSI. In yetother examples, the pressure is 700 PSI. In certain examples, thepressure is 710 PSI. In other examples, the pressure is 720 PSI. In yetother examples, the pressure is 730 PSI. In some other examples, thepressure is 740 PSI. In certain examples, the pressure is 750 PSI. Inyet other examples, the pressure is 760 PSI. In some examples, thepressure is 770 PSI. In yet other examples, the pressure is 780 PSI. Incertain examples, the pressure is 790 PSI. In other examples, thepressure is 800 PSI. In yet other examples, the pressure is 810 PSI.

In other examples, the pressure is 820 PSI. In certain aforementionedexamples, the pressure is 830 PSI. In still others, the pressure is 840PSI. In some other examples, the pressure is 850 PSI. In certainexamples, the pressure is 860 PSI. In yet other examples, the pressureis 870 PSI. In some examples, the pressure is 880 PSI. In yet otherexamples, the pressure is 890 PSI. In certain examples, the pressure is900 PSI. In other examples, the pressure is 910 PSI. In yet otherexamples, the pressure is 920 PSI. In some examples, the pressure is 930PSI. In other examples, the pressure is 940 PSI. In still others, thepressure is 950 PSI. In some other examples, the pressure is 960 PSI. Incertain examples, the pressure is 970 PSI. In yet other examples, thepressure is 980 PSI. In some examples, the pressure is 990 PSI. In yetother examples, the pressure is 1000 PSI.

In some examples, the garnet-based setter plates are useful forimparting beneficial surface properties to the sintered film. Thesebeneficial surface properties include flatness and conductivity usefulfor battery applications. These beneficial properties also includepreventing Li evaporation during sintering. These beneficial propertiesmay also include preferencing a particular garnet crystal structure.

In certain methods disclosed herein, the inert setter plates areselected from porous zirconia, graphite or conductive metal plates. Insome of these methods, the inert setter plates are porous zirconia. Insome other of these methods, the inert setter plates are graphite. Inyet other methods, the inert setter plates are conductive metal plates.

b. Partial Pressure of Oxygen

In some examples, the sintering methods additionally comprisescontrolling the oxygen concentration in the atmosphere in contact withthe sintering garnet material. In some examples, the partial pressure ofoxygen is controlled by flowing a mixture of Argon, Hydrogen, and Water(i.e., H₂O) in contact with the sintering garnet material. In someexamples, the partial pressure of oxygen is controlled by adjusting theflow rates of either the Argon, Hydrogen, or water, or the flow rates ofall three gases or any combinations of these gases. In some examples,the partial pressure of oxygen is 2E-1 (i.e., 20% O₂). In some otherexamples, the partial pressure of oxygen is 1E-2. In some examples, thepartial pressure of oxygen is 1E-3. In other examples, the partialpressure of oxygen is 1E-4. In some other examples, the partial pressureof oxygen is 1E-5. In some examples, the partial pressure of oxygen is1E-6. In other examples, the partial pressure of oxygen is 1E-7. In someother examples, the partial pressure of oxygen is 1E-8. In someexamples, the partial pressure of oxygen is 1E-9. In other examples, thepartial pressure of oxygen is 1E-10. In some other examples, the partialpressure of oxygen is 1E-11. In some examples, the partial pressure ofoxygen is 1E-3. In other examples, the partial pressure of oxygen is1E-12. In some other examples, the partial pressure of oxygen is 1E-13.In other examples, the partial pressure of oxygen is 1E-14. In someother examples, the partial pressure of oxygen is 1E-15. In someexamples, the partial pressure of oxygen is 1E-16. In other examples,the partial pressure of oxygen is 1E-17. In some other examples, thepartial pressure of oxygen is 1E-18. In some examples, the partialpressure of oxygen is 1E-19. In other examples, the partial pressure ofoxygen is 1E-20. In some other examples, the partial pressure of oxygenis 1E-21. In some examples, the partial pressure of oxygen is 1E-22. Inother examples, the partial pressure of oxygen is 1E-23. In some otherexamples, the partial pressure of oxygen is 1E-24. In some examples, thepartial pressure of oxygen is 1E-25.

i. Milling Methods

As described herein, several recited methods include methods stepsrelated to mixing and, or, method steps related to milling. Millingincludes ball milling. Milling also includes milling methods that useinert solvents such as, but not limited to, ethanol, isopropanol,toluene, ethyl acetate, methyl acetate, acetone, acetonitrile, orcombinations thereof. Depending on the material milled, the solvents maynot be inert. In some of these examples, milling includes milling withsolvents such as, but not limited to, ethanol, isopropanol, toluene,ethyl acetate, methyl acetate, acetone, acetonitrile, or combinationsthereof.

In some examples, the milling is ball milling. In some examples, themilling is horizontal milling. In some examples, the milling is attritormilling. In some examples, the milling is immersion milling. In someexamples, the milling is high energy milling. In some examples, the highenergy milling process results in a milled particle size distributionwith d₅₀ 100 nm. In some examples, the milling is immersion milling.

In some examples, high energy milling process is used to achieve aparticle size distribution with d % of about 100 nm. In some examples,the solvent is toluene. In some examples, the solvent is isopropylalcohol (IPA), In some examples, the solvent is ethanol. In someexamples, the solvent is diacetone alcohol. In some examples, thesolvent is a polar solvents suitable for achieving the recited d₅₀ size.

In some examples, the milling includes high energy wet milling processwith 0.3 mm yttria stabilized zirconium oxide grinding media beads. Insome examples, ball milling, horizontal milling, attritor milling, orimmersion milling can be used. In some examples, using a high energymilling process produces a particle size distribution of about d₅₀˜100nm.

V. EXAMPLES

In the examples described herein, the subscript values in the productlithium stuffed garnets formed by the methods herein represent elementalmolar ratios of the precursor chemicals used to make the claimedcomposition.

a. Example 1 Flux Deposition of Li Conducting Ceramic

In some example, a preformed garnet material, i.e., seed crystal, isused to prepare other garnet materials. In this Example, 100 grams (g)of Li₇La₃ZrO₁₂ is mixed with 31.03 g of Li₂CO₃, 58.65 g of La₂O₃, and29.57 g ZrO₂. The resulting mixture was ball milled in isopropanol fortwenty four hours. The mixture was then dried and subsequently calcinedat 900° C. for twelve hours and then sintered at 1100° C. for twelvehours. The product resulting was milled again in isopropanol to reducethe average particle size to 1 μm.

b. Example 2 Flux Deposition of Li Conducting Ceramic

In this example, thin film garnet electrolytes that are 3 μm to 50 μmare prepared. In this example, the garnet precursors wereLiOH/Li₂CO₃/LiO₂/La₂O₃/ZrO₂. The precursors were milled using 0.3 mmyttria stabilized zirconium oxide grinding media beads. The milledprecursors were dispersed in a slurry formulation, and the slurry wasdeposited onto a metal foil. The slurry was then dried, pressure wasapplied to the film with plates, and heated to sinter the componentstherein. Doped compositions were prepared using AlNO₃ and Al₂O₃ assources of Al. Nb₂O₅ was a source of Nb, and Ta₂O₅ was used as a sourceof Ta.

The garnet precursor slurry was deposited onto a metal foil substrate. Apiece of nickel of about 0.5 mil thickness was used as a base substrate.A cleaning method was used to prepare the substrate. In one case, an IPAsolvent was used to remove residual organics on the surface of the metalfoil. Other surface cleaning methods such as UV Ozone treatment, coronadischarge treatment, atmospheric plasma treatment, and chemicaltreatments (light acid/base solutions like ammonium hydroxide orcitric/acetic acid) may also be used to prep the surface for slurrycoating. Using a doctor blade, film thickness between 3 um and 100 umwere achieved with adjustment of the doctor blade gap.

Next, the deposited film was dried. Once the film was dried, thedeposited film was calendered to achieve a dense film prior to anythermal steps. Depending on the starting thickness, up to 50% thicknessreduction was achieved after the calender step. The next step involvedthe application of pressure on the films. Pressures up to 20 MPa wereapplied.

Next, a sintering process was performed. The size of the sintered graindepended on the degree of sintering performed. Sintering was performedat a temperature range of about 900° C. to 1200° C. with only 15-90minutes of dwell time.

The sintering process increases the density and uniformity of the garnetthin film. FIG. 7 is an XRD graph of a thin garnet film processed assuch. Confirmation of the garnet phase is demonstrated through XRD inFIG. 7.

c. Example 3 Densification with Bismuth Flux

Lithium stuffed garnet powder was densified in this example using a fluxcomposed of 1:1 mixture of Li₂CO₃ and B₂O₃.

FIG. 52 shows the resultant density of lithium stuffed garnet films as afunction of the heating conditions of the flux: 900° C., 30 minutes,(bottom curve); 950° C., 30 minutes, (second from bottom curve); 950°C., 6 hours, (third from bottom curve); 100° C., 30 minutes, (topcurve).

d. Example 4 Making Fine Grained Li Ion Conducting Garnet Ceramics

In this example, LiOH, La₂O₃. ZrO₇ and Al(NO₃)₃.9H₂0 were combined invarious ratios and mixed by dry ball milling for 8 hours. The mixturewas then calcined at 800-1000° C. in alumina crucibles in air for 4 to 8hours.

As noted above, to prepare a Li₇La₃Zr₂O₁₂.0.35Al₂O₃ phase, the abovereactants were mixed so that the molar ratios of Li:La:Zr:Al₂ was7:3:2:0.35.

Composition C, the XRD of which is shown in FIG. 49, was prepared byreacting dry milled (Yttria-stabilized Zirconia milling media for about2-10 hours and 80 mesh sieve) 64.6 grams (g) LiOH with 184.5 g La₂O₃,93.9 g ZrO₂, and 96.3 g Al(NO₃)₃.9H₂O. The reactant powders were driedat 120° C. for about an hour. The powders were calcined in aluminacrucibles between 800-1000° C. In alumina crucibles in air for 4 to 8hours.

The product was attrition milled with solvent until the d₅₀ particlesize was ˜300 nm (as determined by light scattering) and dried to yielddry powder. Pellets were formed by mixing the dry powder with 4% w/wpoly vinyl butyral, in isopropanol, removing the isopropanol, and 80mesh sieving.

13 mm diameter, approximately 1.2 to 1.4 mm thick, pellets were pressedfrom this binder-coated powder under about 3 metric tons. Pellets wereplaced between setter places and sintered in a tube furnace with dryflowing Argon (Ar; 315 sccm flow rate). The sintering included heatsintering between 150-180° C. for 1-4 hours, then 300-350° C. for 1-4hours, and then 1000-1200° C. for 3-9 hours, then cooled.

Mass and dimensions of sintered pellets were measured to determinegeometrical density and scanning electron microscopy was used todetermine grain size on fractured cross sections.

FIG. 9 shows a map of the compositional space studied. The compositionalvariables included Lithium and Aluminum content. The Lanthanum andZirconium ratios were maintained at 3:2 for the entire study. FIG. 9shows that there exists a zone of high conductivity (>10⁻⁴S/cm) in thestudied phase space. The zone is larger for the lower sinteringtemperature, (1075° C. compared to 1150° C.). The high temperature,short dwell condition (1200° C. 15 mins) does not yield as goodconductivity as the samples prepared at lower temperatures. Severalcompositions disclosed in the present work result in high conductivity,e.g., compositions A, B, C, D (as shown in FIG. 9).

Composition A is characterized by Li_(6.3)La₃Zr₂O₁₂.0.35Al₂O₃.

Composition B is characterized by Li_(6.3)La₃Zr₂O₁₂.0.67Al₂O₃.

Composition C is characterized by Li₇La₃Zr₂O₁₂.0.67Al₂O₃.

Composition D is characterized by Li₇La₃Zr₂O₁₂.Al₂O₃.

FIG. 10 shows cross sections through the phase space map (FIG. 9) andalso the associated density and grain size.

The processing and sintering of garnet ceramics, set forth herein,employed relatively short reaction times and modest temperatures ascompared to other known techniques. FIG. 12 shows that for a given Aldoping level, there exists a Lithium level below which the garnet grainsize remains relatively low (i.e., <10 um) and beyond which grain sizebecomes too high i.e., >100 um).

FIG. 11 shows a comparative analysis of known garnet compositions withthose described herein. It is clear that these other studies operate ina “high Lithium” region for all studied Aluminum contents. Moreover, themajority of known garnet sintering temperatures were 1200° C. or greaterand had long processing times (e.g., greater than 10 hours) whichresults large grain growth, and which are not compatible with thepowders, films, and devices set forth in the instant application. Theinstant application shows unexpected short processing dwell times andunexpected low temperature processing conditions which result in garnetfilms having conductivity values suitable for use in secondary batteryapplications.

The examples set forth herein demonstrate that small grain size can beachieved in the lithium-lanthanum-zirconia-alumina system by limitingthe Li content and the sintering temperature. The particular compositionof Li, Al=6.3, 0.67 (composition B) is exemplary, since it is found tobe small grained after 1075° C. sintering but becomes large grainedafter 1150° C. This indicates how specific the chosen processingconditions are the methods described herein are. It is noted that if the1075° C. processing temperature is used, compositions A, B, C, and D inthe current work result in the rather unique combination of low grainsize and high conductivity (>10⁻⁴ S/cm).

FIG. 12 shows certain example scanning electron microscopy images ofcertain lithium stuffed garnets having fine grains as described hereinand sintered at lower temperatures, e.g., 1075° C.

FIG. 13 shows certain x:y ratios of Li:Al in Li_(x)La₃Zr₂O₁₂.yAl₂O₃wherein the bulk conductivity is greater than 3*10⁻⁴ S/cm.

FIG. 14 shows a range of compositions that can be made using the methodsset forth herein and the densities associated with these compositions.

FIG. 49 shows the XRD for Composition C.

e. Example 5 Impedance Measurement for Pellet of Composition C

Electrical transport properties were determined by polishing pellets toroughly 1 mm thickness and then sputtering Platinum (Pt) electrodes oneither side. Impedance spectra of electrode pellets were measured atseveral temperatures.

FIG. 50 shows the impedance of a polished pellet of Composition C. R1 isattributed to bulk conduction. R2 is attributed to interfacialimpedance. Electrode effect is attributed to blocking of Li ions at thePt electrode. Total resistance equals R1+R2. Conductivity is calculatedfrom

$R = \frac{l}{\sigma \; A}$

wherein R is resistance in Ohms (Ω), L is pellet thickness in cm, A iselectrode area in cm², and σ is conductivity in S/cm. For FIG. 51, L is0.094 cm; A is 0.385 cm²: Total conductivity is 2.9×10⁻⁴ S/cm; bulkconductivity is 5.1×10⁻⁴ S/m.

The reported conductivity include all resistances observed in theimpedance spectra.

f. Example 6 Full Cell Charge-Discharge

An electrochemical cell was assembled having a pellet of Garnet withcomposition C, 2 μm Li evaporated negative electrode on one side of thepellet, and a positive electrode on the other side of the pelletcomprising NCA with conductive additives including carbon and a sulfurcontaining catholyte.

A charge discharge curve is shown in FIG. 51.

g. Example 7 Plating and Stripping

A Lithium plating and striping protocol for plating and stripping Li ona Garnet Bi-layer thin film: Ni|G|eLi. Initial open circuit voltage is˜2.5V. Initially a current is passed at a rate of 1 mA/cm² to graduallydrop the cell voltage towards zero. When voltage falls below zero (t=500sec) Li begins to plate on the Nickel interface. At t=800 sees, currentis stopped. Voltage rests at 0V indicating a symmetric cell (i.e., Li onboth sides). At t=900 secs, a 4 step cycle is initialed and repeatedseveral times. 1 mA/cm² current is again passed to continue plating for2 mins. Sample is allowed to rest for Imin. Then 1 mA/cm² is passed inopposite direction to strip Li for 2 mins. Sample is allowed to rest forImin for again. After 10 iterations of this sequence. Li is completelyremoved from the Ni side by a final stripping current and consequentlythe voltage rises rapidly once the Lithium is depleted (t=2800 secs)

Results are shown in FIG. 48.

h. Example 8 Powders, Slurries, Tapes, and Bilayer Films

Powder lithium stuffed garnet were prepared according to Example 4:Making Fine Grained Li Ion Conducting Garnet Ceramics.

Powders were into formulated as a slurry by milling the powder. 20 g ofdried milled powder was milled with YSZ milling media and toluene,ethanol, and a dispersant phosphate ester. Then, 8 g of the powder wasmixed with of a 33% w/w solution of polyvinyl butyral in toluene and 4 gof plasticizer di-butyl Phthalate).

The slurry was tape casted onto a silicone coated substrate using adoctor blade (blade height is set to ˜0.250 μm) and had a dried tapethickness of around 70 μm.

Electrodes were screen printed using an electrode ink having 12.74 g ofNi powder and 3.64 g of a 7% w/w solution of ethyl cellulose in asolvent and using a 400 mesh screen. Ink was dried in air and also in anoven at 120° C.

Bilayer films were sintered using setter plates in a tube furnace with aflowing Argon, H₂ and H₂O. Oxygen partial pressure in the tube iscontrolled by adjusting the relative flow of these three species. Binderremoved at 500° C. Films sintered at about 1000-1200° C.

Bilayer films prepared are shown in FIG. 54, FIG. 55, and FIG. 56.

i. Example 9 Powders, Slurries, Tapes, and Bilayer Films

Powders comprising Li₇Li₃Zr₂O₁₂ (LLZ) and alumina were prepared bymixing I molar equivalent of Al₂O₃ and the requisite molar ratios ofLithium Hydroxide, Zirconium Oxide, Lanthanum Oxide and AluminumNitrate.

Powders was dried in an oven for 45 minutes to 1 hour and then drymilled for 8 hours using a ball milling technique with 25% media byvolume. The media was separated using sieves and then calcined in air at900° C. for 6 hours to produce garnet powder.

A slurry was then prepared using 300 g of this calcined garnet powderwhich was then attrition milled in 300 g of isopropanol ortoluene:ethanol (4:1) in the presence of 30 g of a dispersant until theparticle size (d₅₀) was 300-400 nm.

35 g of this slurry was added to 2.65 g of dispersant (e.g., Rhodoline4160) and milled with zirconia media (¼ by volume of bottle) for 8hours. 1.75 g of the plasticizer dibutyl phthalate and 1.75 g of abinder was added to the slurry and milled for another 12 hours. 1.5 g oftoluene was added and mixed for another 2 hours.

A green tape was prepared by casting tape onto mylar tape using a doctorblade set-up and a 20 mil blade height setting. The film was dried, andthen separate film from Mylar. Ni was screen-printed as Ni ink onto thedried film. Discs of the film were cut for sintering.

Samples were sintered by placing the cut films with Ni thereupon betweenceramic setter places and sintered inside a tube furnace. The furnacewas heated 5° C./min to 200° C. In wet Ar wet and held at 200° C. for 4hours, then heated to 600° C. at 5° C./min and held for 4 hours, thenheated to 1100° C. at 10° C./min and held for 1 hour in 315 sccm Ar and10 sccm Ar/H₂. Furnace was then cooled.

j. Example 10 Bilayer Films

A bilayer half cell was prepared by evaporating ˜2 um Li on one side ofthe garnet side, as shown in FIG. 59.

Impedance (EIS) and plating were tested. Plating test commenced with EISusing a linear voltage sweep to get the voltage to 0V (vs. OCV). Afterrest, initial plating was at 200 uA. Plating and Stripping was at 100 uAwith rest periods in-between. A final strip at 200 uA was thenperformed. Results shown in FIGS. 53 and 61.

k. Example 11 Free Standing Films

Free standing film were formed from powders, prepared by batching therequisite molar ratios of Lithium Hydroxide, Zirconium Oxide, LanthanumOxide and Aluminum Nitrate to form LLZ w/1 molar amount of Al₂O₃. Powderwas dried in an oven for 45 minutes to 1 hour, then dry milled for 8hours using a ball milling technique with 25% media by volume, the mediawas separated then the powder was calcined in air at 900° C. for 6 hoursto produce the garnet powder.

A slurry was prepared using 300 g of this calcined garnet powder,attrition milled in 200 g isopropanol and 30 g of a dispersant until theparticle size (d₅₀) was 300-400 nm. 60 g of the slurry was added to 5.35g of dispersant (e.g., Rhodoline 4160) and milled with zirconia mediafor 8 hours. 3.57 g of plasticizer dibutyl phthalate was added to 3.57 gbinders and milled for another 12 hours at low rpm, then 6.5 g oftoluene was added and mixed for 2 hours.

A green tape was cast tape manually on mylar tape using a doctor bladeset-up and a 20 mil blade height setting. The film was dried andseparate film from the Mylar. The films were cut to form discs forsintering.

Sintering of the discs occurred between ceramic setters in a tubefurnace

Samples were sintered by placing the cut films between ceramic setterplaces and sintered inside a tube furnace. The furnace was heated 5°C./min to 200° C. In wet Ar wet and held at 200° C. for 4 hours, thenheated to 600° C. at 5° C./min and held for 4 hours, then heated to1100° C. at 10° C./min and held for 1 hour in 315 sccm Ar and 10 sccmAr/H₂. Furnace was then cooled.

l. Example 12 Reactive Sintering

Powders were prepared comprising LLZ w/1 molar equivalent of Al₂O₃ bybatching the requisite molar ratios of Lithium Hydroxide, ZirconiumOxide, Lanthanum Oxide and Aluminum Nitrate. Powder was dried in an ovenfor 45 minutes to 1 hr, then dry milled for 8 hours using a ball millingtechnique with 25% media by volume, separating from media using sieves,and then reactive sintering this mixture. Powder was calcined in air at900° C. for 6 hours to produce garnet powder.

A slurry was prepared using 300 g of calcined garnet powder withreactive sintering precursors, attrition milled in 300 g Toluene ethanol(4:1) or Diacetone, with 30 g of a dispersant until the particle size(d₅₀) was 300-400 nm.

10 g of this slurry was mixed in a flactek mixer for 15 minutes, then0.2 g binder was added to the slurry and mixed for another 15 minutes.

A green Tape was prepared by casting the slurry onto Ni foil using adoctor blade set-up and a 5 or 10 mil blade height setting. The film wasdried and cut into discs.

Sintering occurred by placing the film between ceramic setters in tubefurnace.

Samples were sintered by placing the cut films between ceramic setterplaces and sintered inside a tube furnace. The furnace was heated 5°C./min to 200° C. In wet Ar wet and held at 200° C. for 4 hours, thenheated to 600° C. at 5° C./min and held for 4 hours, then heated to1100° C. at 10° C./min and held for 1 hour in 315 sccm Ar and 10 sccmAr/H₂. Furnace was then cooled.

m. Example 13 Low Area Specific Resistance (ASR)

In this example, ceramic setters were compared to metallic setters. Theceramic setters resulted in garnet film that had lower ASR. Films weresintered according to Example 12, in one case with Pt setter plates andin another case with ceramic setter plates.

As shown in FIG. 61, the films sintered with ceramic setter plates had alower ASR.

Results are also shown in the below Table.

TABLE 1 Total conductivity, 60 C. Sintering style R1 (Ohms) R2 (Ohms)(S/cm) Pt plates 220 2840 8.49E−05 Pt plates 230 293 4.97E−04 Ceramicplates 323 131 5.72E−04 Ceramic plates 261 98 7.24E−04 Pt plates 1813326 7.41E−05 Pt plates powder 288 399 3.78E−04 Ceramic plates 237 718.44E−04 Ceramic plates 334 136 5.53E−04

These examples show the compatibility of garnet with Li anodes and thelower tendency to form a solid electrolyte interfacial high resistancelayer.

n. Example 14 Low Area Specific Resistance (ASR) at Pellet Surface

Pellets of lithium stuffed garnet were prepared as detailed above.Pellets were sintered in either Ar, or a mixture of Ar/H₂, or in Air.Impedance results are shown in FIG. 62. ASR lower for Ar and Ar/H₂ thanfor Air.

Although the foregoing embodiments have been described in some detailfor purposes of clarity of understanding, it will be apparent thatcertain changes and modifications may be practiced within the scope ofthe appended claims. It should be noted that there are many alternativeways of implementing the processes, systems and apparatus of the presentembodiments. Accordingly, the present embodiments are to be consideredas illustrative and not restrictive, and the embodiments are not to belimited to the details given herein.

1. A method for making a lithium (Li) ion conducting thin film, themethod comprising: providing a reaction mixture comprisinglithium-stuffed garnet or lithium-stuffed garnet chemical precursors;milling the mixture; providing a slurry comprising the mixture and asolvent; depositing the slurry onto a substrate to form a thin film; andsintering the thin film between setter plates to form a lithium stuffedsintered garnet thin film.
 2. The method of claim 1, wherein theprecursors comprise one or more members selected from the groupconsisting of LiOH, Li₂O, ZrO₂, La₂O₃, Al₂O₃, AlNO₃, Nb₂O₅, Ta₂O₅,Li₂C₂O₅, AlN₂O₅-hydrate, AlN₂O₅.9H₂O, and combinations thereof. 3.(canceled)
 4. The method of claim 1, further comprising depositing anadditional layer of the mixture or the slurry onto the lithium stuffedgarnet film to form a multilayer.
 5. The method of claim 4, furthercomprising sintering the multilayer between setter plates to form alithium-stuffed sintered garnet thin film. 6.-7. (canceled)
 8. Themethod of claim 1, wherein the milling step results in precursorparticle sizes that have a d₅₀ of 1 μm or less.
 9. (canceled)
 10. Themethod of claim 8, wherein the particle sizes have a d₅₀ of about 50-200nm.
 11. The method of claim 7, wherein the milling comprises solventmilling and wherein the solvent is a polar solvent.
 12. The method ofclaim 11, wherein the solvent is selected from the group consisting oftoluene, isopropanol, ethanol, acetic acid, diacetone alcohol,acetonitrile, ethyl acetate, methyl ethyl ketone, and combinationsthereof.
 13. (canceled)
 14. The method of claim 1, wherein the substratecomprises a metal selected from the group consisting of Al, Ni, Cu, Au,Ag, Fe, steel, stainless steel, Li, alloys thereof, and combinationsthereof.
 15. The method of claim 1, comprising calcining the film priorto sintering the film and at a temperature from about 300° C. to about1000° C.
 16. (canceled)
 17. The method of claim 1, comprising the stepof depositing the slurry onto a substrate to form a film andsubsequently evaporating the solvent prior to sintering the film. 18.The method of claim 1, wherein the reaction mixture further comprises amember selected from the group consisting of NASICON, LISICON, and atungsten bronze.
 19. The method of claim 1, wherein the reaction mixturefurther comprises a binder selected from the group consisting of fromthe group consisting of polypropylene (PP), polyvinyl butyral (PVB),polyvinylpyrrolidone (PVP), atactic polypropylene (aPP), isotactivepolypropylene, ethylene propylene rubber (EPR), ethylene pentenecopolymer (EPC), polyisobutylene (PIB), ZEON™, styrene butadiene rubber(SBR), polyolefins, polyethylene-co-poly-1-octene (PE-co-PO),PE-co-poly(methylene cyclopentane) (PE-co-PMCP), stereoblockpolypropylenes, polypropylene polymethylpentene copolymer and silicone.20. (canceled)
 21. The method of claim 1, wherein depositing comprisestape casting or slot-die coating.
 22. The method of claim 1, comprisingsintering the film at about 1100° C. for about 15 minutes to about 2hours. 23.-39. (canceled)
 40. A lithium stuffed sintered garnet thinfilm prepared by the method of claim
 1. 41. (canceled)
 42. (canceled)43. The method of claim 1, wherein the lithium (Li) ion conducting thinfilm is a free standing sintered garnet thin film.
 44. The method ofclaim 1, further comprising providing a rechargeable battery comprisingthe Li-stuffed garnet solid electrolyte.
 45. A method for making alithium (Li) ion conducting thin film, the method comprising: providinga reaction mixture comprising lithium-stuffed garnet or lithium-stuffedgarnet chemical precursors; milling the mixture; providing a slurrycomprising the mixture and a solvent; depositing the slurry onto asubstrate to form a thin film; and sintering the film by applyingpressure to the thin film with a setter plate to form a lithium stuffedgarnet thin film.
 46. The method of claim 45, wherein applying pressurecomprises applying the pressure applied by the weight of the setterplate resting on top of the thin film.
 47. The method of claim 45,wherein the precursors comprise one or more members selected from thegroup consisting of LiOH, Li₂O, ZrO₂, La₂O₃, Al₂O₃, AlNO₃, Nb₂O₅, Ta₂O₅,Li₂C₂O₅, AlN₂O₅-hydrate, AlN₂O₅.9H₂O, and combinations thereof.
 48. Themethod of claim 45, further comprising depositing an additional layer ofthe mixture or the slurry onto the lithium stuffed garnet film to form amultilayer.
 49. The method of claim 48, further comprising sintering themultilayer between setter plates to form a lithium stuffed garnet thinfilm.
 50. The method of claim 45, wherein the substrate comprises ametal selected from the group consisting of Al, Ni, Cu, Au, Ag, Fe,steel, stainless steel, Li, alloys thereof, and combinations thereof.51. The method of claim 45, comprising calcining the film prior tosintering the film and at a temperature from about 300° C. to about1000° C.
 52. The method of claim 45, wherein the reaction mixturefurther comprises a binder selected from the group consisting of fromthe group consisting of polypropylene (PP), polyvinyl butyral (PVB),polyvinylpyrrolidone (PVP), atactic polypropylene (aPP), isotactivepolypropylene ethylene propylene rubber (EPR), ethylene pentenecopolymer (EPC), polyisobutylene (PIB), ZEON™, styrene butadiene rubber(SBR), polyolefins, polyethylene-co-poly-1-octene (PE-co-PO),PE-co-poly(methylene cyclopentane) (PE-co-PMCP), stereoblockpolypropylenes, polypropylene polymethylpentene copolymer and silicone.53. The method of claim 45, comprising sintering the film at about 1100°C. for about 15 minutes to about 2 hours.
 54. A nanostructured lithiumstuffed garnet prepared by the method of claim
 45. 55. The method ofclaim 45, further comprising providing a rechargeable battery comprisingthe Li-stuffed garnet solid electrolyte.